Reaction of carbon black with diazonium salts, resultant carbon black products and their uses

ABSTRACT

Processes for preparing a carbon black product having an organic group attached to the carbon black. In one process at least one diazonium salt reacts with a carbon black in the absence of an externally applied electric current sufficient to reduce the diazonium salt. In another process at least one diazonium salt reacts with a carbon black in a protic reaction medium. Carbon black products which may be prepared according to process of the invention are described as well as uses of such carbon black products in plastic compositions, rubber compositions, paper compositions, and textile compositions.

This application is a continuation of U.S. patent application Ser. No.10/139,264 filed May 3, 2002, now U.S. Pat. No. 6,740,151, which is acontinuation of U.S. patent application Ser. No. 09/257,237 filed Feb.25, 1999, now U.S. Pat. No. 6,494,946, which is a continuation of U.S.patent application Ser. No. 09/105,007, filed Jun. 26, 1998, now U.S.Pat. No. 6,042,643, which is a continuation of prior U.S. patentapplication Ser. No. 08/572,525, filed Dec. 14, 1995, now U.S. Pat. No.5,851,280, which is a continuation-in-part of U.S. patent applicationSer. No. 08/356,660, filed Dec. 15, 1994, now abandoned, and areincorporated in their entirety by reference herein.

FIELD OF THE INVENTION

This invention relates to a process for the preparation of carbon blackproducts. The process involves reacting a diazonium salt with a carbonblack to yield a carbon black product having an organic group attachedto the carbon black. The invention also relates to new carbon blackproducts and their uses.

BACKGROUND OF THE INVENTION

Much effort has been expended over the last several decades to modifythe surface chemistry of carbon black. While it is possible to depositphysically adsorbed material onto the surface of carbon black,permanently changing the surface chemistry of carbon black issubstantially more difficult.

Some processes for chemically changing the surface of carbon black areknown and used commercially. For example, it is well known that a carbonblack surface can be oxidized with a variety of treating agents. Surfaceoxidation is used to make some commercial products. Sulfonation usingsulfuric acid or chlorosulfuric acid and halogenation of a carbon blacksurface are also known. Some known methods for grafting polymers to thecarbon black surface are reviewed by Tsubakowa in Polym. Sci., Vol. 17,pp 417-470, 1992. See also U.S. Pat. No. 4,014,844 which grafts polymersonto carbon black by contacting the carbon black with the polymer andheating.

U.S. Pat. No. 3,479,300 describes carbon catalyst compositions and aprocess for their production. The catalyst compositions are prepared bytreating carbon particles with an alkali or alkaline earth metal andsubsequently treating the resulting carbon/metal composition with asolvating ether. The carbon portions of the catalytic compositions canbe reacted with various reagents, including organic compounds, toproduce carbon compositions.

U.S. Pat. No. 3,043,708 describes modified carbon blacks havinghydrocarbon groups chemically attached to the surface of the carbonblack. The modified carbon blacks are prepared by reacting carbon blackwith an alkylating agent in the presence of a Friedel-Crafts typereaction catalyst. The hydrocarbon groups which reportedly can attach tothe surface of the carbon black include aliphatic and aromatic groups. Amodified carbon black containing aryl groups attached to the surface ofa carbon black is reported as being preparable by reacting a halogenatedcarbon black with an aromatic hydrocarbon in the presence of aFriedel-Crafts type catalyst. U.S. Pat. No. 3,025,259 describes rubbercompositions containing the modified carbon blacks of U.S. Pat. No.3,043,708.

U.S. Pat. No. 3,335,020 describes modified carbon blacks where thecarbon black is treated with benzene which is then polymerized on thecarbon black. To prepare these modified carbon blacks, benzene andcarbon black are mixed with a Lewis. Acid catalyst under anhydrousconditions for about ten minutes. The benzene on the carbon black isthen polymerized to parapolyphenyl by means of a combinationco-catalyst-oxidizing agent and is reportedly thereby bonded to thecarbon black.

U.S. Pat. Nos. 2,502,254 and 2,514,236 describe the manufacture ofpigments containing carbon black. U.S. Pat. No. 2,502,254 reports thathighly dispersed pigments suitable for mass pigmentation of viscose canbe obtained by generating an azo pigment in the presence of carbonblack.

The pigment is produced by coupling a diazotized amine and another usualintermediate for a yellow, orange, or red pigment in the presence ofcarbon black in one or the other of the aqueous solutions of which themixing brings about the coupling. U.S. Pat. No. 2,514,236 reports thatthis process can also prepare a chocolate brown pigment by coupling onemolecular proportion of a tetrazotized benzidine with two molecularproportions of an arylmethyl pyrazolone in the presence of carbon black.

PCT Patent Application No. WO 92/13983 describes a process for modifyingthe surfaces of carbon-containing materials by electrochemical reductionof diazonium salts. The process is reportedly applicable, in particular,to carbon plates and carbon fibers for composite materials.Carbon-containing materials modified by the process are also described.Electrochemical reduction of diazonium salts containing functionalizedaryl radicals to covalently modify carbon surfaces is also described inDelmar et al., J. Am. Chem. Soc. 1992, 114, 5883-5884.

According to WO 92/13983, the process for modifying the surface of acarbon-containing material consists of grafting an aromatic group to thesurface of this material by electrochemical reduction of a diazoniumsalt including this aromatic group. The carbon-containing material isplaced in contact with a diazonium salt solution in an aprotic solventand is negatively charged with respect to an anode which is also incontact with the diazonium salt solution. Use of a protic solvent isreported to prevent the electrochemical process from producing theintended product as a result of reducing the diazonium triple bond toyield a hydrazine.

Despite the technology discussed above, there remains a need to modifythe surface chemistry of carbon black and impart desired properties tothe carbon black.

SUMMARY OF THE INVENTION

Accordingly, the present invention relates to processes for preparing acarbon black product having an organic group attached to the carbonblack. One process comprises the step of reacting at least one diazoniumsalt with a carbon black in the absence of an externally appliedelectric current sufficient to reduce the diazonium salt. Anotherprocess comprises the step of reacting at least one diazonium salt witha carbon black in a protic reaction medium.

Other embodiments of the invention relate to novel carbon blackproducts, which may be prepared according to a process of the invention.The carbon black products may be used in the same applications asconventional carbon blacks. Such uses include, but are not limited to,plastic compositions, aqueous inks, aqueous coatings, rubbercompositions, paper compositions, and textile compositions.

The description which follows sets out additional features andadvantages of the invention. These functions will be apparent from thatdescription or may be learned by practice of the invention as described.The objectives and other advantages will be realized and attained by theprocesses, products, and compositions particularly pointed out in thedescription below and the appended claims.

DETAILED DESCRIPTION

Processes for Preparing a Carbon Black Product

A first embodiment of the invention provides processes for preparing acarbon black product having an organic group attached to the carbonblack. One process involves the reaction of at least one diazonium saltwith a carbon black in the absence of an externally applied currentsufficient to reduce the diazonium salt. That is, the reaction betweenthe diazonium salt and the carbon black proceeds without an externalsource of electrons sufficient to reduce the diazonium salt. Mixtures ofdifferent diazonium salts may be used in the process of the invention.This process can be carried out under a variety of reaction conditionsand in any type of reaction medium, including both protic and aproticsolvent systems or slurries.

In another process, at least one diazonium salt reacts with a carbonblack in a protic reaction medium. Mixtures of different diazonium saltsmay be used in this process of the invention. This process can also becarried out under a variety of reaction conditions.

Preferably, in both processes, the diazonium salt is formed in situ. Ifdesired, in either process, the carbon black product can be isolated anddried by means known in the art. Furthermore, the resultant carbon blackproduct can be treated to remove impurities by known techniques. Thevarious preferred embodiments of these processes are discussed below andare shown in the examples.

Any carbon black may be used in the processes of this invention. Theresulting carbon black products are useful in applications known forconventional carbon blacks. The properties of the carbon blacks areselected based upon the intended application. More importantly, theprocesses of this invention can be used to provide carbon black productshaving advantageous properties not associated with conventional carbonblacks.

The processes of the invention can be carried out under a wide varietyof conditions and in general are not limited by any particularcondition. The reaction conditions must be such that the particulardiazonium salt is sufficiently stable to allow it to react with thecarbon black. Thus, the processes can be carried out under reactionconditions where the diazonium salt is short lived. As the examplesbelow illustrate, the reaction between the diazonium salt and the carbonblack occurs, for example, over a wide range of pH and temperature. Theprocesses can be carried out at acidic, neutral, and basic pH.Preferably, the pH ranges from about 1 to 9. The reaction temperaturemay preferably range from 0° C. to 100° C.

Diazonium salts, as known in the art, may be formed for example by thereaction of primary amines with aqueous solutions of nitrous acid. Ageneral discussion of diazonium salts and methods for their preparationis found in Morrison and Boyd, Organic Chemistry, 5th Ed., pp. 973-983,(Allyn and Bacon, Inc. 1987) and March, Advanced Organic Chemistry:Reactions, Mechanisms, and Structures, 4th Ed., (Wiley, 1992). Accordingto this invention, a diazonium salt is an organic compound having one ormore diazonium groups.

In the processes of the invention, the diazonium salt may be preparedprior to reaction with the carbon black or, more preferably, generatedin situ using techniques known in the art. In situ generation alsoallows the use of unstable diazonium salts such as alkyl diazonium saltsand avoids unnecessary handling or manipulation of the diazonium salt.In particularly preferred processes of this invention, both the nitrousacid and the diazonium salt are generated in situ. Each of thesevariations is shown in the examples below.

A diazonium salt, as is known in the art, may be generated by reacting aprimary amine, a nitrite and an acid. The nitrite may be any metalnitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite,or zinc nitrite, or any organic nitrite such as for exampleisoamylnitrite or ethylnitrite. The acid may be any acid, inorganic ororganic, which is effective in the generation of the diazonium salt.Preferred acids include nitric acid, HNO₃, hydrochloric acid, HCl, andsulfuric acid, H₂SO₄.

The diazonium salt may also be generated by reacting the primary aminewith an aqueous solution of nitrogen dioxide. The aqueous solution ofnitrogen dioxide, NO₂/H₂O, provides the nitrous acid needed to generatethe diazonium salt.

Generating the diazonium salt in the presence of excess HCl may be lesspreferred than other alternatives because HCl is corrosive to stainlesssteel. Generation of the diazonium salt with NO₂/H₂O has the additionaladvantage of being less corrosive to stainless steel or other metalscommonly used for reaction vessels. Generation using H₂SO₄/NaNO₂ orHNO₃/NaNO₂ are also relatively non-corrosive.

In general, generating a diazonium salt from a primary amine, a nitrite,and an acid requires two equivalents of acid based on the amount ofamine used. In an in situ process, the diazonium salt can be generatedusing one equivalent of the acid. When the primary amine contains astrong acid group, adding a separate acid may not be necessary in theprocesses of the invention. The acid group or groups of the primaryamine can supply one or both of the needed equivalents of acid. When theprimary amine contains a strong acid group, preferably either noadditional acid or up to one equivalent of additional acid is added to aprocess of the invention to generate the diazonium salt in situ. Aslight excess of additional acid may be used. One example of such aprimary amine is para-aminobenzenesulfonic acid (sulfanilic acid).Others are shown in the examples below.

In general, diazonium salts are thermally unstable. They are typicallyprepared in solution at low temperatures, such as 0-5° C., and usedwithout isolation of the salt. Heating solutions of some diazonium saltsmay liberate nitrogen and form either the corresponding alcohols inacidic media or the organic free radicals in basic media.

However, to accomplish the process of the invention, the diazonium saltneed only be sufficiently stable to allow reaction with the carbonblack. Thus, the processes of the present invention can be carried outwith some diazonium salts otherwise considered to be unstable andsubject to decomposition. Some decomposition processes may compete withthe reaction between the carbon black and the diazonium salt and mayreduce the total number of organic groups attached to the carbon black.Further, the reaction may be carried out at elevated temperatures wheremany diazonium salts may be susceptible to decomposition. Elevatedtemperatures may also advantageously increase the solubility of thediazonium salt in the reaction medium and improve its handling duringthe process. However, elevated temperatures may result in some loss ofthe diazonium salt due to other decomposition processes.

The processes of the invention can be accomplished by adding thereagents to form the diazonium salt in situ, to a suspension of carbonblack in the reaction medium, for example, water. Thus, a carbon blacksuspension to be used may already contain one or more reagents togenerate the diazonium salt and the process of the inventionaccomplished by adding the remaining reagents. Some permutations of suchprocesses are shown in the examples below.

Reactions to form a diazonium salt are compatible with a large varietyof functional groups commonly found on organic compounds. Thus, only theavailability of a diazonium salt for reaction with a carbon black limitsthe processes of the invention.

The processes of this invention can be carried out in any reactionmedium which allows the reaction between the diazonium salt and thecarbon black to proceed. Preferably, the reaction medium is asolvent-based system. The solvent may be a protic solvent, an aproticsolvent, or a mixture of solvents. Protic solvents are solvents, likewater or methanol, containing a hydrogen attached to an oxygen ornitrogen and thus are sufficiently acidic to form hydrogen bonds.Aprotic solvents are solvents which do not contain an acidic hydrogen asdefined above. Aprotic solvents include, for example, solvents such ashexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile. For adiscussion of protic and aprotic solvents see Morrison and Boyd, OrganicChemistry, 5th Ed., pp. 228-231, (Allyn and Bacon, Inc. 1987).

The processes of this invention are preferably carried out in a proticreaction medium, that is, in a protic solvent alone or a mixture ofsolvents which contains at least one protic solvent. Preferred proticmedia include, but are not limited to water, aqueous media containingwater and other solvents, alcohols, and any media containing an alcohol,or mixtures of such media.

According to the processes of the invention, the reaction between adiazonium salt and a carbon black can take place with any type of carbonblack, for example, in fluffy or pelleted form. In one embodimentdesigned to reduce production costs, the reaction occurs during aprocess for forming carbon black pellets. For example, a carbon blackproduct of the invention can be prepared in a dry drum by spraying asolution or slurry of a diazonium salt onto a carbon black.Alternatively, the carbon black product can be prepared by pelletizing acarbon black in the presence of a solvent system, such as water,containing the diazonium salt or the reagents to generate the diazoniumsalt in situ. Aqueous solvent systems are preferred. Accordingly,another embodiment of the invention provides a process for forming apelletized carbon black comprising the steps of: introducing a carbonblack and an aqueous slurry or solution of a diazonium salt into apelletizer, reacting the diazonium salt with the carbon black to attachan organic group to the carbon black, and pelletizing the resultingcarbon black having an attached organic group. The pelletized carbonblack product may then be dried using conventional techniques.

In general, the processes of the invention produce inorganicby-products, such as salts. In some end uses, such as those discussedbelow, these by-products may be undesirable. Several possible ways toproduce a carbon black product according to a process of the inventionwithout unwanted inorganic by-products or salts are as follows:

First, the diazonium salt can be purified before use by removing theunwanted inorganic by-product using means known in the art. Second, thediazonium salt can be generated with the use of an organic nitrite asthe diazotization agent yielding the corresponding alcohol rather thanan inorganic salt. Third, when the diazonium salt is generated from anamine having an acid group and aqueous NO₂, no inorganic salts areformed. Other ways may be known to those of skill in the art.

In addition to the inorganic by-products, a process of the invention mayalso produce organic by-products. They can be removed, for example, byextraction with organic solvents. Other ways may be known to those ofskill in the art.

Carbon Black Products

The reaction between a diazonium salt and a carbon black according to aprocess of this invention forms a carbon black product having an organicgroup attached to the carbon black. The diazonium salt may contain theorganic group to be attached to the carbon black. Thus, the presentinvention relates to carbon black products having an organic groupattached to the carbon black, particularly those prepared by a processof this invention. It may be possible to produce the carbon blackproducts of this invention by other means known to those skilled in theart.

The organic group may be an aliphatic group, a cyclic organic group, oran organic compound having an aliphatic portion and a cyclic portion. Asdiscussed above, the diazonium salt employed in the processes of theinvention can be derived from a primary amine having one of these groupsand being capable of forming, even transiently, a diazonium salt. Theorganic group may be substituted or unsubstituted, branched orunbranched. Aliphatic groups include, for example, groups derived fromalkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylicacids, and carbohydrates. Cyclic organic groups include, but are notlimited to, alicyclic hydrocarbon groups (for example, cycloalkyls,cycloalkenyls), heterocyclic hydrocarbon groups (for example,pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), arylgroups (for example, phenyl, naphthyl, anthracenyl, and the like), andheteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl,furyl, indolyl, and the like). As the steric hinderance of a substitutedorganic group increases, the number of organic groups attached to thecarbon black from the reaction between the diazonium salt and the carbonblack may be diminished.

When the organic group is substituted, it may contain any functionalgroup compatible with the formation of a diazonium salt. Preferredfunctional groups include, but are not limited to, R, OR, COR, COOR,OCOR, carboxylate salts such as COOLi, COONa, COOK, COO⁻NR₄ ⁺, halogen,CN, NR₂, SO₃H, sulfonate salts such as SO₃Li, SO₃Na, SO₃K_(i) SO₃ ⁻NR₄⁺, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, PO₃H₂, phosphonate saltssuch as PO₃HNa and PO₃Na₂, phosphate salts such as OPO₃HNa and OPO₃Na₂,N═NR, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, SSO₃ ⁻ salts, SO₂NRR′, SO₂SR,SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl)2-(1,3-dithiolanyl), SOR, and SO₂R. R and R′, which can be the same ordifferent, are independently hydrogen, branched or unbranched C₁-C₂₀substituted or unsubstituted, saturated or unsaturated hydrocarbon,e.g., alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl,substituted or unsubstituted heteroaryl, substituted or unsubstitutedalkylaryl, or substituted or unsubstituted arylalkyl. The integer kranges from 1-8 and preferably from 2-4. The anion X⁻ is a halide or ananion derived from a mineral or organic acid. Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherew is an integer from 2 to 6 and x and z are integers from 1 to 6.

The carbon black product can comprise a carbon black and at least oneorganic group having a) an aromatic group and b) a cationic group,wherein at least one aromatic group of the organic group is attached tothe carbon black. The organic group can be, for example X⁻ R₃N⁺CH₂COAr,wherein R is a substituted or unsubstituted C₁-C₁₀ alkyl, Ar isphenylene or naphthylene, and X⁻ is a halide or an anion derived from amineral or organic acid.

A preferred organic group is an aromatic group of the formula A_(y)Ar—,which corresponds to a primary amine of the formula A_(y)ArNH₂. In thisformula, the variables have the following meanings: Ar is an aromaticradical such as an aryl or heteroaryl group. Preferably, Ar is selectedfrom the group consisting of phenyl, naphthyl, anthracenyl,phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl, andbenzothiazolyl; A is a substituent on the aromatic radical independentlyselected from a preferred functional group described above or A is alinear, branched or cyclic hydrocarbon radical (preferably containing 1to 20 carbon atoms), unsubstituted or substituted with one or more ofthose functional groups; and y is an integer from 1 to the total numberof —CH radicals in the aromatic radical. For instance, y is an integerfrom 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 whenAr is anthracenyl, phenanthrenyl, or biphenyl, or 1 to 4 when Ar ispyridinyl.

In the above formula, specific examples of R and R′ are NH₂—C₆H₄—,CH₂CH₂—C₆H₄—NH₂, CH₂—C₆H₄—NH₂, and C₆H₅.

Another preferred set of organic groups which may be attached to thecarbon black are organic groups substituted with an ionic or anionizable group as a functional group. An ionizable group is one whichis capable of forming an ionic group in the medium of use. The ionicgroup may be an anionic group or a cationic group and the ionizablegroup may form an anion or a cation.

Ionizable functional groups forming anions include, for example, acidicgroups or salts of acidic groups. The organic groups, therefore, includegroups derived from organic acids. Preferably, when it contains anionizable group forming an anion, such an organic group has a) anaromatic group and b) at least one acidic group having a pKa of lessthan 11, or at least one salt of an acidic group having a pKa of lessthan 11, or a mixture of at least one acidic group having a pKa of lessthan 11 and at least one salt of an acidic group having a pKa of lessthan 11. The pKa of the acidic group refers to the pKa of the organicgroup as a whole, not just the acidic substituent. More preferably, thepKa is less than 10 and most preferably less than 9. Preferably, thearomatic group of the organic group is directly attached to the carbonblack. The aromatic group may be further substituted or unsubstituted,for example, with alkyl groups. More preferably, the organic group is aphenyl or a naphthyl group and the acidic group is a sulfonic acidgroup, a sulfinic acid group, a phosphonic acid group, or a carboxylicacid group. Examples of these acidic groups and their salts arediscussed above. Most preferably, the organic group is a substituted orunsubstituted sulfophenyl group or a salt thereof; a substituted orunsubstituted (polysulfo)phenyl group or a salt thereof; a substitutedor unsubstituted sulfonaphthyl group or a salt thereof; or a substitutedor unsubstituted (polysulfo)naphthyl group or a salt thereof. Apreferred substituted sulfophenyl group is hydroxysulfophenyl group or asalt thereof.

Specific organic groups having an ionizable functional group forming ananion (and their corresponding primary amines for use in a processaccording to the invention) are p-sulfophenyl (p-sulfanilic acid),4-hydroxy-3-sulfophenyl (2-hydroxy-5-amino-benzenesulfonic acid), and2-sulfoethyl (2-aminoethanesulfonic acid). Other organic groups havingionizable functional groups forming anions are shown in the examplesbelow.

Amines represent examples of ionizable functional groups that formcationic groups. For example, amines may be protonated to form ammoniumgroups in acidic media. Preferably, an organic group having an aminesubstituent has a pKb of less than 5. Quaternary ammonium groups (—NR₃⁺) and quaternary phosphonium groups (—PR₃ ⁺) also represent examples ofcationic groups. Preferably, the organic group contains an aromaticgroup such as a phenyl or a naphthyl group and a quaternary ammonium ora quaternary phosphonium group. The aromatic group is preferablydirectly attached to the carbon black. Quaternized cyclic amines, andeven quaternized aromatic amines, can also be used as the organic group.Thus, N-substituted pyridinium compounds, such as N-methylpyridyl, canbe used in this regard. Examples of organic groups include, but are notlimited to, (C₅H₄N)C₂H₅ ⁺, C₆H₄(NC₅H₅)⁺, C₆H₄COCH₂N(CH₃)₃ ⁺,C₆H₄COCH₂(NC₅H₅)⁺, (C₅H₄N)CH₃ ⁺, and C₆H₄CH₂N(CH₃)₃ ⁺.

An advantage of the carbon black products having an attached organicgroup substituted with an ionic or an ionizable group is that the carbonblack product may have increased water dispersibility relative to thecorresponding untreated carbon black. As shown in the Examples, waterdispersibility of a carbon black product increases with the number oforganic groups attached to the carbon black having an ionizable group orthe number of ionizable groups attached to a given organic group. Thus,increasing the number of ionizable groups associated with the carbonblack product should increase its water dispersibility and permitscontrol of the water dispersibility to a desired level. It can be notedthat the water dispersibility of a carbon black product containing anamine as the organic group attached to the carbon black may be increasedby acidifying the aqueous medium.

Because the water dispersibility of the carbon black products depends tosome extent on charge stabilization, it is preferable that the ionicstrength of the aqueous medium be less than 0.1 molar. More preferably,the ionic strength is less than 0.01 molar.

When such a water dispersible carbon black product is prepared by aprocess of the invention, it is preferred that the ionic or ionizablegroups be ionized in the reaction medium. The resulting product solutionor slurry may be used as is or diluted prior to use. Alternatively, thecarbon black product may be dried by techniques used for conventionalcarbon blacks. These techniques include, but are not limited to, dryingin ovens and rotary kilns. Overdrying, however, may cause a loss in thedegree of water dispersibility.

In addition to their water dispersibility, carbon black products havingan organic group substituted with an ionic or an ionizable group mayalso be dispersible in polar organic solvents such as dimethylsulfoxide(DMSO), and formamide. In alcohols such as methanol or ethanol, use ofcomplexing agents such as crown ethers increases the dispersibility ofcarbon black products having an organic group containing a metal salt ofan acidic group.

Aromatic sulfides encompass another group of preferred organic groups.Carbon black products having aromatic sulfide groups are particularlyuseful in rubber compositions. These aromatic sulfides can berepresented by the formulas Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ orA-(CH₂)_(q)S_(K)(CH₂)_(r)Ar″ wherein Ar and Ar′ are independentlysubstituted or unsubstituted arylene or heteroarylene groups, Ar″ is anaryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substitutedaryl groups would include substituted alkylaryl groups. Preferredarylene groups include phenylene groups, particularly p-phenylenegroups, or benzothiazolylene groups. Preferred aryl groups includephenyl, naphthyl and benzothiazolyl. The number of sulfurs present,defined by k preferably ranges from 2 to 4. Particularly preferredaromatic sulfide groups are bis-para-(C₆H₄)—S₂—(C₆H₄)— andpara-(C₆H₄)—S₂—(C₆H₅). The diazonium salts of these aromatic sulfidegroups may be conveniently prepared from their corresponding primaryamines, H₂N—Ar—S_(k)—Ar′—NH₂ or H₂N—Ar—S_(k)—Ar″.

Another preferred set of organic groups which may be attached to thecarbon black are organic groups having an aminophenyl, such as(C₆H₄)—NH₂, (C₆H₄)—CH₂—(C₆H₄)—NH₂, (C₆H₄)—SO₂—(C₆H₄)—NH₂.

Uses of the Carbon Black Products

The carbon black products of this invention may be used in the sameapplications as conventional carbon blacks. The organic groups attachedto the carbon black, however, can be used to modify and improve theproperties of a given carbon black for a particular use. If desiredthese organic groups attached to the carbon black may also be chemicallychanged using means known in the art into other groups for a particularuse. For example, an acid group can be converted to its salt or itsamide.

Carbon black products according to the invention have been prepared andevaluated in a number of end use applications. These uses include, forexample, plastic compositions, aqueous inks, aqueous coatings, rubbercompositions, paper compositions and textile compositions. The followingparagraphs describe these uses generally and examples of each are shownbelow.

The carbon black products of this invention may be used as pigments orcolorants in a plastic material. The carbon black products of theinvention can also be used to impart conductivity to a plastic material.The carbon black products of the invention may give an increased rate ofdispersion or improved quality of dispersion over the correspondinguntreated carbon blacks. These improvements offer an economic advantagein plastic manufacture and in value of the finished product,respectively. As shown in Examples 47-62, using carbon black products ofthe invention may improve impact strength of the plastic. Thus, theinvention relates to an improved plastic composition comprising aplastic and a carbon black, the improvement comprising the use of acarbon black product according to the invention.

As with conventional carbon blacks, the carbon black products can beused with a variety of plastics, including but not limited to plasticsmade from thermoplastic resins, thermosetting resins, or engineeredmaterials, for example, composites. Typical kinds of thermoplasticresins include: (1) acrylonitrile-butadiene-styrene (ABS) resins; (2)acetals; (3) acrylics; (4) cellulosics; (5) chlorinated polyethers; (6)fluorocarbons, such as polytetrafluoroethylene (TFE),polychlorotrifluoroethylene (CTFE), and fluorinated ethylene propylene(FEP); (7) nylons (polyamides); (8) polycarbonates; (9) polyethylenes(including copolymers); (10) polypropylenes (including copolymers); (11)polystyrenes; (12) vinyls (polyvinyl chloride); (13) thermoplasticpolyesters, such as polyethylene terephthalate or polybutyleneterephthalate; (14) polyphenylene ether alloys; and blends and alloys ofthe above with rubber modifiers. Typical thermosetting resins include:(1) alkyds; (2) allylics; (3) the aminos (melamine and urea); (4)epoxies; (5) phenolics; (6) polyesters; (7) silicones; and (8)urethanes.

Generally, the carbon black product is added like any other pigment tothe plastic used to form a plastic premix. This can be done, forexample, in a dry mix or a melt stage. The carbon black products of theinvention may be used in combination with other conventional additivesin plastic compositions. According to the invention, the term plasticcomposition includes, but is not limited to, any plastic material,article, goods, surface, fabric, sheet, and the like For example,plastic materials include automotive parts, siding for homes, liners forswimming pools, roofing materials, packaging materials, and any varietyof other household or industrial items.

The carbon black products of this invention are also useful in aqueousink formulations. The water-dispersible carbon black products discussedabove are particularly preferred for this use. Thus, the inventionprovides an improved ink composition comprising water and a carbonblack, the improvement comprising the use of a carbon black productaccording to the invention. Other known aqueous ink additives may beincorporated into the aqueous ink formulation.

In general, an ink consists of four basic components: (1) a colorant orpigment, (2) a vehicle or varnish which functions as a carrier duringprinting, (3) additives to improve printability drying, and the like,and (4) solvents to adjust viscosity, drying and the compatibility ofthe other ink components. For a general discussion on the properties,preparation and uses of aqueous inks, see The Printing Manual, 5th Ed.,Leach et al, Eds. (Chapman and Hall, 1993). Various aqueous inkcompositions are also disclosed, for example, in U.S. Pat. Nos.2,833,736, 3,607,813, 4,104,833, 4,308,061, 4,770,706, and 5,026,755.

The carbon black products of the invention, either as predispersion oras a solid, can be incorporated into an aqueous ink formulation usingstandard techniques. Use of a water dispersible carbon black product ofthe invention provides a significant advantage and cost savings byreducing or eliminating the milling steps generally used with otherconventional carbon blacks.

Flexographic inks represent a group of aqueous ink compositions.Flexographic inks generally include a colorant, a binder, and a solvent.The carbon black products of the invention, particularly thewater-dispersible carbon products, are useful as flexographic inkcolorants. Example 101 shows the use of a carbon black product of theinvention in an aqueous flexographic ink formulation.

The carbon black products of the invention can be used in aqueous newsinks. For example, an aqueous news ink composition may comprise water,the carbon black products of the invention, a resin and conventionaladditives such as antifoam additives or a surfactant.

The carbon black products of the invention may also be used in aqueouscoating compositions such as paints or finishes. The use of the waterdispersible carbon black products discussed above in such coatingcompositions is preferred. Thus, an embodiment of the invention is animproved aqueous coating composition comprising water, resin and acarbon black, the improvement comprising the use of a carbon blackproduct according to the invention. Other known aqueous coatingadditives may be incorporated the aqueous coating compositions. See, forexample, McGraw-Hill Encyclopedia of Science & Technology, 5th Ed.(McGraw-Hill, 1982). See also U.S. Pat. Nos. 5,051,464, 5,319,044,5,204,404, 5,051,464, 4,692,481, 5,356,973, 5,314,945, 5,266,406, and5,266,361.

The carbon black products of the invention, either as a predispersion oras a solid, can be incorporated into an aqueous coating compositionusing standard techniques. Use of a water dispersible carbon blackproduct provides a significant advantage and cost savings by reducing oreliminating the milling steps generally used with other conventionalcarbon blacks. Examples 102 and 103 below show the use of carbon blackproducts according to the invention in aqueous automotive topcoatformulations.

The carbon black products of the invention may also be used in papercompositions. Preferred carbon black products for this use are the waterdispersible carbon black products discussed above. Accordingly, theinvention relates to an improved paper product comprising paper pulp anda carbon black, the improvement comprising the use of a carbon blackaccording to the invention.

The carbon black products of the invention, either as a solid or apredispersion, can be incorporated into paper pulp using standardpapermaking techniques as with conventional carbon blacks. Use of awater dispersible carbon black product discussed above may provide asignificant advantage and cost savings by reducing or eliminating thesteps generally used to disperse other conventional carbon blacks.Example 100 shows a paper product using a carbon black product accordingto the invention.

The paper products of the invention may incorporate other known paperadditives such as sizing agents, retention aids, fixatives, fillers,defoamers, deflocculating agents, and the like. Advantageously, thewater dispersible carbon black products discussed above are retainedmore efficiently at low loading levels when compared to the untreatedcarbon black when retention aids and acidic or alkaline sizing agentsare used.

The carbon black products of the invention may also be used, as withconventional carbon blacks, as pigments, fillers, and reinforcing agentsin the compounding and preparation of rubber compositions. Accordingly,the invention relates to an improved rubber composition containingrubber and a carbon black, the improvement comprising the use of acarbon black product according to the invention. The properties of thecarbon black are important factors in determining the performance of therubber composition containing a carbon black.

Carbon blacks, for example, are useful in the preparation of rubbervulcanizates such as those in tires. It is generally desirable in theproduction of tires to utilize carbon blacks which produce tires withsatisfactory abrasion resistance and hysteresis performance. Thetreadwear properties of a tire are related to abrasion resistance. Thegreater the abrasion resistance, the greater the number of miles thetire will last without wearing out. The hysteresis of a rubber compoundmeans the difference between the energy applied to deform a rubbercompound, and the energy released as the rubber compound recovers to itsinitial undeformed state. Tires with lower hysteresis values reducerolling resistance and therefore are able to reduce the fuel consumptionof the vehicle utilizing the tire. Thus, it is particularly desirable tohave carbon black products capable of imparting greater abrasionresistance and lower hysteresis in tires.

The carbon black products of this invention are useful in both naturaland synthetic rubber compositions or mixtures of natural and syntheticrubbers. Carbon black products containing aromatic sulfides as theorganic group, which are discussed above, are preferred for this use.Particularly preferred for use in rubber compositions are carbon blackproducts having an attached aromatic sulfide organic group of theformula —(C₆H₄)—S_(k)—(C₆H₄)—, where k is an integer from 1 to 8, andmore preferably where k ranges from 2 to 4. The carbon black products ofthe invention can be used in rubber compositions which are sulfur-curedor peroxide-cured.

The carbon black products may be mixed with natural or synthetic rubbersby normal means, for example by milling. Generally, amounts of thecarbon black product ranging from about 10 to about 250 parts by weightcan be used for each 100 parts by weight of rubber in order to impart asignificant degree of reinforcement. It is, however, preferred to useamounts varying from about 20 to about 100 parts by weight of carbonblack per 100 parts by weight of rubber and especially preferred is theutilization of from about 40 to about 80 parts of carbon black per 100parts of rubber.

Among the rubbers suitable for use with the present invention arenatural rubber and its derivatives such as chlorinated rubber. Thecarbon black products of the invention may also be used with syntheticrubbers such as: copolymers of from about 10 to about 70 percent byweight of styrene and from about 90 to about 30 percent by weight ofbutadiene such as copolymer of 19 parts styrene and 81 parts butadiene,a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of43 parts styrene and 57 parts butadiene and a copolymer of 50 partsstyrene and 50 parts butadiene; polymers and copolymers of conjugateddienes such as polybutadiene, polyisoprene, polychloroprene, and thelike, and copolymers of such conjugated dienes with an ethylenicgroup-containing monomer copolymerizable therewith such as styrene,methyl styrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,alkyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone,methyl vinyl either, alphamethylene carboxylic acids and the esters andamides thereof such as acrylic acid and dialkylacrylic acid amide; alsosuitable for use herein are copolymers of ethylene and other high alphaolefins such as propylene, butene-1 and pentene-1.

The rubber compositions of the present invention can therefore containan elastomer, curing agents, reinforcing filler, a coupling agent, and,optionally, various processing aids, oil extenders, and antidegradents.In addition to the examples mentioned above, the elastomer can be, butis not limited to, polymers (e.g., homopolymers, copolymers, andterpolymers) manufactured from 1,3 butadiene, styrene, isoprene,isobutylene, 2,3-dimethyl-1,3 butadiene, acrylonitrile, ethylene,propylene, and the like. It is preferred that these elastomers have aglass transition point (Tg), as measured by DSC, between −120° C. and 0°C. Examples of such elastomers include poly(butadiene),poly(styrene-co-butadiene), and poly(isoprene).

Advantageously, the carbon black products of the present invention canimpart improved abrasion resistance and/or reduced hysteresis to rubbercompositions containing them. Examples 104-116 show the use of carbonblack products of the invention in various rubber compositions andvarious properties of those compositions.

The carbon black products of this invention may also be used to colorfibers or textiles. Preferred carbon black products for this use are thewater dispersible carbon black products discussed above. Accordingly,the invention relates to improved fiber and textile compositionscomprising a fiber or textile and a carbon black, the improvementcomprising the use of a carbon black according to the invention. Fiberssuitable for use comprise natural and synthetic fibers such as cotton,wool, silk, linen, polyester and nylon. Textiles suitable for usecomprise natural and synthetic fibers such as cotton, wool, silk, linen,polyester and nylon. Preferably natural fibers and textiles comprisingcotton, wool, silk and linen are used.

The carbon black products of the present invention may be colored bymeans known in the art to color fibers and textiles with, for example,direct and acid dyes. For a general discussion of coloring with dyes,see Kirk-Othmer Encyclopedia of Chemical Technology, Vol 8 pp 280-350“Dyes, Application and Evaluation” (John Wiley and Sons, 1979). Use of awater dispersible carbon black product discussed above provides a methodfor coloring these materials with a lightfast colorant.

The following examples are intended to illustrate, not limit, theclaimed invention.

EXAMPLES

Analytical Methods

Unless otherwise specified, BET nitrogen surface areas obtainedaccording to ASTM D-4820 are used for surface area measurements. CTABareas and iodine numbers are used occasionaly and were obtainedaccording to ASTM D-3765 and D-1510, respectively. DBPA data wereobtained according to ASTM D-2414.

Volatile content was determined as follows. A carbon black sample wasdried to constant weight at 125° C. A 45 mL sample of the dry carbonblack was placed in a covered 50 mL crucible that had been dried at 950°C. and heated in a muffle furnace for 7 minutes at 950° C. The volatilecontent is expressed as the percentage of weight lost by the carbonsample.

The following procedure was used in various Examples below to determinethe aqueous residue of carbon black products according to this inventionand untreated carbon blacks. The carbon black product (5 g) was shakenwith 45 g of water for 5 minutes. The resulting dispersion was pouredthrough a screen and rinsed with water until the washings werecolorless. A 325 mesh screen was used unless indicated otherwise. Afterdrying the screen, the weight of residue on the screen was determinedand expressed as a percentage of the carbon black product used in thetest.

For the Examples relating to rubber compositions, modulus, tensilestrength, and elongation were determined according to ASTM D-412. ShoreA hardness was determined according to ASTM D-2240-86.

The abrasion data on the rubber compositions were determined using anabrader which is based on a Lambourn type machine. Abrasion rates (cubiccentimeter/centimeter travel) were measured at 14% and 21% slip. Theslip is based on the relative velocity between the sample wheel andgrindstone. In the following examples, the abrasion index is the ratioof the abrasion rate of a control compositon divided by the abrasionrate of a rubber compostion prepared with a carbon black product of theinvention.

Tan δ was measured with a Rheometrics Dynamic Spectrometer Model RDS-2at a constant frequency of 10 Hz, a constant temperature, and in theshear mode of strain. Strain sweeps were run from 0.2% to 120% DSA.Measurements were taken at five points per decade and the maximum Tan δwas reported.

Bound rubber was determined as follows: A 0.5 g sample of an uncuredrubber composition containing a rubber and a known amount of a carbonblack was placed in a wire cage and submerged in toluene at roomtemperature. After standing for one day, the sample was placed in freshtoluene, and allowed to stand for three additional days at roomtemperature. The sample was then removed, dried in an oven, and weighed.The weight of the carbon black was subtracted from weight of the samplebefore and after toluene treatment to give a value for the amount ofrubber in each sample. The weight of the sample after toluene treatment,adjusted for the weight of the carbon black and other insolubleingredients in the composition, represents the amount of insolublerubber remaining. Bound rubber was expressed as the percentage of theweight of insoluble rubber in the sample after standing in tolueneversus the amount of rubber in the original sample.

Example 1 Preparation of a Carbon Black Product with Preformed DiazoniumSalt

This example illustrates the preparation of a carbon black product ofthe present invention. A pelleted carbon black with a surface area of230 m²/g and a DBPA of 64 ml/100 g was used. An aqueous solution of4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60 g of water at room temperature.Bubbles were released. After stirring for 60 minutes, the resultingcarbon black product was removed by filtration, washed with water andsubjected to Soxhlet extraction with tetrahydrofuran (THF) overnight.Analysis of the carbon black product after extraction showed that itcontained 2.49% bromine, compared to <0.01% for the untreated pelletedcarbon black prior to use in this example. This corresponds to 78% ofthe bromophenyl groups being attached to the carbon black product.Therefore, the carbon black product has 0.31 mmol/g of attachedbromophenyl groups.

Examples 2-4 Preparation of a Carbon Black Product with PreformedDiazonium Salt

These examples illustrate additional methods for the preparation ofcarbon black products of the present invention. The pelleted carbonblack used in Example 1 was used in Examples 2-4. An aqueous solution of4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60.5 g of a 0.826% NaOH solution atthe temperature indicated. Bubbles were released. After stirring for thetime indicated in the following table, the resulting carbon blackproduct was removed by filtration, washed with water and subjected toSoxhlet extraction with THF overnight. Bromine analysis of the productafter extraction showed that a substantial fraction of the bromophenylgroups had been attached to the carbon black product. This shows thatthe preparation of carbon black products according to the invention canbe carried our at different times, temperatures and pHs.

Portion of Bromophenyl Temperature, Time, Bromine, bromophenyl groups,Example C. min. % retained, % mmol/g 2 <5 5 1.88 59 0.24 3 <5 60 2.15 670.27 4 Ambient 60 2.45 77 0.31

Example 5 Preparation of a Carbon Black Product with a Diazonium SaltGenerated In Situ

This example further illustrates the preparation of a carbon blackproduct of the present invention. A fluffy carbon black with a surfacearea of 560 m2/g, a DBPA of 90 ml/100 g and a volatile content of 9.5%was used. Fifty grams of the fluffy carbon black were added to asolution of 8.83 g of sulfanilic acid dissolved in 420 g of water. Theresulting suspension was cooled to room temperature. Nitrogen dioxide(5.16 g) was dissolved in 30 g of ice cold water, and then added to thefluffy carbon black suspension over a period of several minutes andstirred rapidly, to produce 4-sulfobenzenediazonium inner salt in situ,which reacts with the fluffy carbon black. The resulting dispersion wasdried in an oven at 125° C., leaving only the carbon black product. Thecarbon black product contained 1.94% sulfur after Soxhlet extractionwith ethanol overnight, compared to 0.24% sulfur for the untreatedcarbon black. This corresponds to attaching 52% of the p-C6H4SO3- groupsto the carbon black product. Therefore, the carbon black product had0.53 mmol/g of attached p-C₆H₄SO₃— groups.

Example 6 Preparation of a Carbon Black Product

This example illustrates another method for the preparation of a carbonblack product of the present invention. Sulfanilic acid (2.13 g) wasdissolved in 90 g of water with stirring and heating. Ten grams of acarbon black with a CTAB surface area of 350 m2/g and a DBPA of 120ml/100 g were added. The mixture was cooled to room temperature andisobutyl nitrite (1.27 g) was added. Bubbles were released.4-Sulfobenzene diazonium hydroxide inner salt was generated in situ andit reacted with the carbon black. The mixture was stirred for 30minutes, and dried in an oven at 125° C. A sample of the resultingcarbon black product that had been subjected to Soxhlet extraction withethanol overnight contained 2.02% sulfur, compared to 0.5% for theuntreated carbon black. Therefore, the carbon black product had 0.48mmol/g of attached p-C₆H₄SO₃— groups.

Example 7 Preparation of a Carbon Black Product in an Aprotic Solvent

This example illustrates the preparation of a treated carbon blackproduct of the present invention in an aprotic solvent. A 0.1 M solutionof tetrabutylammonium hexafluorophosphate in anhydrous acetonitrile wasprepared and allowed to stand overnight over 3A molecular sieves. A 5.4%solution of chlorobenzenediazonium hexafluorophosphate in anhydrousacetonitrile was prepared and allowed to stand overnight over 3Amolecular sieves. A carbon black with a surface area of 230 m2/g and aDBPA of 70 ml/100 g was dried at 150° C. under nitrogen for 4 hours. Thecarbon black (10 g) was stirred into 80 mL of the tetrabutylammoniumhexafluorophosphate solution. The diazonium solution (21 g) was added,and the mixture was stirred for four hours. The carbon black product wasrecovered by filtration and was washed with anhydrous acetonitrile. Alloperations up to this point were carried out in a dry box under an argonatmosphere. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a chlorine contentof 0.76%, compared to 0.02% for the untreated carbon black. Therefore,the carbon black product had 0.21 mmol/g of attached chlorophenylgroups.

Example 8 Preparation of a Carbon Black Product in an Aprotic Solvent

This example illustrates the preparation of a treated carbon blackproduct of the present invention in an aprotic solvent. A carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was heated at950° C. under nitrogen for one hour. A 0.1 M solution oftetrabutylammonium tetrafluoroborate in anhydrous benzonitrile wasprepared and allowed to stand overnight over 3A molecular sieves. Usingglassware dried at 160° C. under argon, the carbon black (6 g) wasstirred into 50 mL of the tetrabutylammonium tetrafluoroborate solution.4-Bromobenzenediazonium tetrafluoroborate was added, and the mixture wasstirred for 15 minutes. The carbon black product was recovered byfiltration and was washed twice with anhydrous benzonitrile and twicewith hexanes. Except for the initial drying of the carbon black, alloperations up to this point were carried out under an argon atmospherein a dry box. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a bromine content of0.85%, compared to <0.01% for the untreated carbon black. Therefore, thecarbon black product had 0.11 mmol/g of attached bromophenyl groups.

Example 9 Preparation of a Carbon Black Product with a Diazonium SaltGenerated In Situ

This example illustrates another method for the preparation of a carbonblack product of the present invention. A fluffy carbon black with asurface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatile contentof 9.5% was used. Fifty grams of the fluffy carbon black were added to asolution of 8.83 g of sulfanilic acid dissolved in 420 g of water. Theresulting suspension was cooled to 30° C. and 4.6 g of concentratednitric acid was added. An aqueous solution containing 3.51 g of sodiumnitrite was then added gradually with stirring, forming4-sulfobenzenediazonium hydroxide inner salt in situ, which reacts withthe fluffy carbon black. The resulting product was dried in an oven at125° C., leaving the carbon black product. The carbon black productcontained 1.97% sulfur after Soxhlet extraction with ethanol overnight,compared to 0.24% sulfur for the untreated fluffy carbon black. Thiscorresponds to attaching 53% of the p-C₆H₄SO₃— groups to the carbonblack product. Therefore, the carbon black product had 0.54 mmol/g ofattached p-C₆H₄SO₃— groups.

Example 10 Preparation of a Carbon Black Product with an AliphaticDiazonium Salt

This example shows another method for the preparation of a carbon blackproduct of the present invention. A fluffy carbon black with a surfacearea of 230 m2/g and a DBPA of 70 ml/100 g was used. Twenty grams ofthis black were added to a solution of 4.9 g of 2-aminoethanesulfonicacid in 180 g of water. Concentrated nitric acid (4.32 g) was added. Asolution of 3.33 g of sodium nitrite in 15 g of water was added slowlywith stirring, forming 2-sulfoethanediazonium nitrate in situ, whichreacted with the fluffy carbon black. A large quantity of bubblesevolved. The product was dried in an oven at 135° C., leaving a carbonblack product. The resulting carbon black product contained 1.68% sulfurafter Soxhlet extraction with ethanol overnight, compared to 0.4% forthe untreated fluffy carbon black. This corresponds to attaching 20% ofthe C₂H₄SO₃— groups to the carbon black product. Therefore, the carbonblack product had 0.40 mmol/g of attached C₂H₄SO₃— groups.

Example 11 Preparation of a Carbon Black Product with a BenzyldiazoniumSalt

This example shows another method for the preparation of a carbon blackproduct of the present invention. A suspension of 0.676 g of4-bromobenzyl amine, 0.60 g of concentrated HCl, 30 g of water and 10.22g of the untreated carbon black used in Example 7 was prepared in an icebath. An aqueous solution containing 0.269 g of sodium nitrite was addedand the resulting suspension was stirred for 15 minutes, forming4-bromophenylmethanediazonium chloride in situ, which reacted with theuntreated carbon black. The product was filtered off, and was subjectedto Soxhlet extraction with THF overnight. The resulting carbon blackproduct contained 0.26% bromine, compared to <0.01% for the untreatedcarbon black product. This shows that 9% of the bromobenzyl groups usedin the example became attached to the carbon black product. Therefore,the carbon black product had 0.031 mmol/g of attached bromobenzylgroups.

Example 12 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. Ten grams of a carbon black with a surface areaof 230 m2/g and a DBPA of 70 ml/100 g was added to a stirring solutionof 0.8 g 4-bromobenzamide and 90 ml of acetone in 90 g of water.Concentrated HCl (0.87 g) was added followed by 0.33 g of NaNO₂.BrC₆H₄CON₂ ⁺ was formed in situ, which reacted with the carbon black.After stirring for 30 minutes, the mixture was allowed to standovernight and was then dried in an oven at 125° C. A sample of theproduct that had been subjected to Soxhlet extraction with THF overnightand dried contained 0.22% bromine, compared to <0.01% bromine for theunreacted carbon black.

Example 13 Preparation of a Carbon Black Product with a PreformedDiazonium Salt in a Pin Pelletizer

This example shows another method for the preparation of a carbon blackproduct of the present invention. A pin pelletizer was charged with 400g of a fluffy carbon black with a surface area of 80 m2/g and a DBPA of85 ml/100 g. A cold suspension of 4-sulfobenzenediazonium hydroxideinner salt prepared from 27.1 g of the sodium salt of sulfanilic acid,10.32 g of sodium nitrite, 29.0 g of concentrated HCl and 293.5 g ofwater and was added to the pelletizer. After pelletizing for 2 minutes,the sample was removed and dried at 115° C. to constant weight. Soxhletextraction with ethanol overnight gave a carbon black product containing1.1% sulfur, compared against 0.8% for the untreated carbon black. Thisshows that 27% of the p-C₆H₄SO₃— groups were attached to the carbonblack product. Therefore, the carbon black product had 0.09 mmol/g ofattached p-C₆H₄SO₃— groups.

Example 14 Preparation of a Carbon Black Product in a Pin Pelletizerwith a Diazonium Salt Generated In Situ

This example illustrates another method for preparing a carbon blackproduct of the present invention. A pin pelletizer was charged with 200g of a carbon black with a CTAB surface area of 350 m2/g and a DBPA of120. A solution of 44.2 g of sodium sulfanilate in 95 μg of water at 70°C. was added and the pelletizer was run for one minute. Twenty grams ofwater was added followed by 39.6 g of concentrated nitric acid. Thepelletizer was run for an additional minute. Twenty grams of water wasadded followed by a solution of 16.76 g of sodium nitrite in 35 g ofwater, forming 4-sulfobenzenediazonium hydroxide inner salt in situ,which reacted with the carbon black. After running the pelletizer forfive minutes, a solution of 11.22 g of sodium hydroxide in 35 g of waterwas added. The pelletizer was run for an additional two minutes and theresulting a carbon black product was subsequently dried. Soxhletextraction with ethanol overnight gave a carbon black product with 3.3%sulfur, compared against 0.5% for the untreated carbon black. This showsthat 77% of the p-C6H4SO3- groups were attached to the carbon blackproduct. Therefore, the carbon black product had 0.88 mmol/g of attachedp-C₆H₄SO₃— groups.

Example 15 Preparation of a Carbon Black Product in a Pin Pelletizerwith a Diazonium Salt Generated In Situ

This example further illustrates the preparation of a carbon blackproduct of the present invention. A pin pelletizer was charged with 200g of a carbon black product with a surface area of 560 m2/g, a DBPA of90 ml/100 g and a volatile content of 9.5%. Water (60 g), concentratednitric acid (25.2 g), sulfanilic acid (40.4 g) and a solution of 19.7 gof sodium nitrite in 35 g of water were added successively; thepelletizer was run for one minute after each addition.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ, andit reacted with the carbon black. After standing for five minutes, theresulting carbon black product was dried at 125° C. A sample of thecarbon black product was subjected to Soxhlet extraction with ethanolovernight. It contained 2.15% sulfur compared to 0.24% for the untreatedcarbon black. This shows that 51% of the p-C₆H₄SO₃— groups were attachedto the carbon black product. Therefore, the carbon black product had0.60 mmol/g of attached p-C₆H₄SO₃— groups.

Example 16 Preparation of a Carbon Black Product in a Pelletizer with aDiazonium Salt Generated In Situ

This example illustrates another method for the preparation of a carbonblack product of the present invention. A carbon black (200 g) with aCTAB surface area of 350 m2/g and a DBPA of 120 ml/100 g and 42.4 gsulfanilic acid were placed in a pin pelletizer. After mixing for 40seconds, a solution of 20.7 NaNO₂ in 150 g of water was then added.4-sulfobenzene diazonium hydroxide inner salt was formed in situ, whichreacted with the carbon black. After mixing for 45 seconds, theresulting carbon black product was dried in an oven at 120° C. A sampleof the product that had been subjected to Soxhlet extraction overnightwith ethanol contained 3.47% sulfur, compared to 0.5% sulfur for theuntreated carbon black product. Therefore, the carbon black product has0.93 mmol/g of attached p-C₆H₄SO₃— groups.

Example 17 Preparation of a Carbon Black Product in a Continuous PinPelletizer with a Diazonium Salt Generated In Situ

This example illustrates another method for preparing a carbon blackproduct of the present invention. A carbon black with a CTAB surfacearea of 133 m2/g and a fluffy DBPA of 190 ml/100 g is introduced into acontinuously operating pin pelletizer at a rate of 100 parts by weightper hour. Simultaneously, a 30% solution of sodium nitrite in water anda suspension containing 5.43% concentrated nitric acid, 8.72% sulfanilicacid and 85.9% water are introduced into the pelletizer. The sodiumnitrite solution is introduced at 16 parts by weight per hour and thesuspension is added at 112 parts by weight per hour.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black in the pelletizer. The material leavingthe pelletizer was the carbon black product. The carbon black productwas dried at 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction with ethanol overnight contained 1.70%sulfur, compared to 0.42% for the untreated carbon black. Therefore, thecarbon black product had 0.40 mmol/g of attached p-C₆H₄SO₃— groups.

Example 18 Preparation of a Carbon Black Product with a Diazonium SaltGenerated In Situ

This example shows another method for preparing a carbon black productof the present invention. In this example, the acid for thediazotization reaction comes from the amine forming the diazonium salt,sulfanilic acid. As a result, no additional acid was required.Sulfanilic acid (2.12 g) was dissolved in 90 g water at 70° C. Thesolution was added to 10 g of a carbon black with a CTAB surface area of350 m2/g and a DBPA of 120 ml/100 g, and cooled to room temperature. Asolution of 1.04 g NaNO₂ in 10 g water was added with stirring.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black to form the carbon black product. Afterstirring for 30 minutes, the resulting dispersion was dried in an ovenat 120° C. A sample of the carbon black product that had been subjectedto Soxhlet extraction with ethanol overnight contained 3.19% sulfur,compared to 0.5% for the untreated carbon black product. Therefore, thecarbon black product had 0.84 mmol/g of attached p-C₆H₄SO₃— groups.

Example 19 Preparation of a Carbon Black Product with a Diazonium SaltGenerated In Situ

This example illustrates another method for the preparation of a carbonblack product of the present invention. In this example, the acid forthe diazotization reaction comes from the amine forming the diazoniumsalt, sulfanilic acid. As a result, no additional acid was required. Acarbon black (10 g) with a CTAB surface area of 350 m2/g and a DBPA of120 ml/100 g was added to a boiling solution of 2.12 g sulfanilic acidin 90 g of water. A solution of 1.04 g of NaNO₂ in 10 g water was addedcautiosly. 4-Sulfobenzene diazonium hydroxide inner salt was formed insitu, which reacted with the carbon black. After stirring for about 20min, the resulting dispersion was dried in an oven at 120° C. A sampleof the product that had been subjected to Soxhlet extraction overnightwith ethanol contained 3.16% sulfur, compared to 0.5% sulfur for theuntreated carbon black. Therefore, the carbon black product had 0.83mmol/g of attached p-C₆H₄SO₃— groups.

Examples 20-30 Aqueous Dispersibility of Carbon Black Products

These examples show that carbon black products of the present inventiondescribed in some earlier examples are more readily dispersed in waterthan the corresponding untreated carbon black.

Residue of Residue of Carbon Black Carbon Black untreated control,Example Product Product, % % 20 Example 5 3.0 6 21 Example 6 0.2 97 22Example 9 0.12 6 23 Example 10 2.1 94 24 Example 13 0.07 81 25 Example14 0.3 97 26 Example 15 0.26 6 27 Example 16 0.6 97 28 Example 17 0.0236 29 Example 18 0.04 97 30 Example 19 0.01 97

Examples 31-34 Preparation and Aqueous Dispersibility of Carbon BlackProducts

These examples show that carbon black products prepared using severaldifferent diazonium salts are more readily dispersed in water than arethe corresponding untreated carbon blacks. In all cases, the untreatedcarbon black used for treatment has a surface area of 230 m2/g and aDBPA of 70 ml/100 g. To prepare the carbon black product, an anilinederivative was dissolved in warm water, the untreated carbon black (CB)was added and the mixture was cooled to room temperature. ConcentratedHCl was added and then a solution of sodium nitrite in water was added,forming a diazonium salt in situ, which reacts with the untreated carbonblack. After stirring for 15 minutes, the resulting dispersions weredried in an oven at 125° C. Residues were determined using the methoddescribed above. The amounts of each component and results are shown inthe following table. The untreated carbon black had a residue of 94%.

Aniline Aniline Residue Example derivative derivative g HCl g NaNO2 g CBg H20 g % 31 5-Amino 2 1.89 1.18 0.85 10.0 100 0.06 Hydroxy benzenesulfonic acid 32 2-Amino benzene 1.73 1.18 0.82 10.0 67 0.14 sulfonicacid 33 3-Aminobenzene 1.72 1.18 0.84 10.4 77 0.16 sulfonic acid 344-Aminoazo- 2.94 2.60 0.83 10.0 71 2.0 benzene-4′ sulfonic acid, Na saltComparative Untreated — — — — — 94

Examples 35-38 Preparation and Dispersibility of Carbon Black Products

These examples show additional carbon black products that are preparedusing different diazonium salts and that are more readily dispersible inwater than the corresponding untreated carbon black. All of theseexamples use naphthyl diazonium salts. In all cases, a carbon black witha surface area of 230 m2/g and a DBPA of 70 ml/100 g was used. Asolution of 7 mmol of the naphthylamine and 0.42 g NaNO₂ in 10.83 gwater was cooled to <5° C. The diazonium salt was formed by the additionof a cold (5° C.) solution of 1.63 g concentrated HCl in 1.63 g water,maintaining the temperature at <5° C. The reaction product was added toa stirring slurry of 10 g of the untreated carbon black in 90 g ofwater. After stirring for an additional 10 minutes, the dispersion wasdried, leaving the carbon black product. Samples of the carbon blackproducts that had been subjected to Soxhlet extraction overnight withethanol were analyzed for sulfur to determine the number of attachednaphthyl groups.

Substituted Sulfur naphthyl groups, Residue Example Naphthylaminederivative % mmol/g % 35 Sodium 5-amino-2- 2.15 0.51 <0.01 naphthalenesulfonate 36 4-Amino-5-hydroxy-2,7- 2.77 0.35 0.02 naphthalenedisulfonic acid, mono potassiumsalt 37 7-Amino-1,3- 3.09 0.40 0.01naphthalene disulfonic acid, mono potassiumsalt 38 Sodium 4-amino-1-1.79 0.40 0.33 naphthalene sulfonate Comparative Untreated 0.5 — 94

Example 39 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example illustrates another method for the preparation of a carbonblack product of the present invention and illustrates that this carbonblack product was more readily dispersible in water than is thecorresponding untreated carbon black. 7-Amino-1,3-naphthalenedisulfonicacid (1.5 g) was dissolved in 90 g warm water. Ten grams of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasadded, and the mixture was cooled to room temperature. A solution of0.42 g NaNO₂ in 5 g water was added with stirring. The diazonium saltwas formed in situ and reacted with the carbon black. Bubbles werereleased. The resulting dispersion was dried in an oven at 125° C.,giving the carbon black product. The carbon black product had a residueof 0.85%, compared to 94% for the untreated carbon black.

Example 40 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example shows that a carbon black product prepared using anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g.5-Amino-2-hydroxy-3-sulfobenzoic acid (2.33 g), 10 g of carbon black and100 g of water were mixed in an ice bath. Cold concentrated HCl (1.18 g)was added, followed gradually by 0.85 g NaNO₂. The diazonium salt wasformed in situ, and reacted with the carbon black. After stirring for 15minutes, the resulting dispersion was dried in an oven at 125° C. toprovide the carbon black product. The 325 mesh residue of the resultingcarbon black product was 0.1%, compared to 94% for the untreated carbonblack.

Example 41 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example shows that a carbon black product prepared with anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The procedure of Example 40 wasfollowed in all respects, except that 4-amino-2′-nitro-4′-sulfodiphenylamine (3.01 g) was used as the diazonium precursor. The resulting carbonblack product had a 325 mesh residue of 0.18%, compared to 94% for theuntreated carbon black.

Example 42 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example shows another preparation of a carbon black product of thepresent invention, and that this carbon black product was more readilydispersible in water than is the correspondingly untreated carbon black.4-Aminophenyl-phosphonic acid (0.90 g) was added to 10 g of ice coldwater. NaOH (0.26 g) was added to dissolve the solid. A cold solution of0.42 g NaNO₂ in 5 g of cold water was added. Concentrated HCl was added(3.83 g) and the solution was stirred at <10° C. for 15 minutes, formingthe corresponding diazonium salt. A cold suspension of 5.02 g of acarbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100 gin 36.2 g of water was added and stirred for 15 minutes. The resultingdispersion was concentrated to dryness under vacuum at room temperaturegiving a carbon black product. This carbon black product dispersesreadily in water, and had a 325 mesh residue of 2.7%, compared to 94%for the untreated carbon black. A sample of the carbon black productthat was dried in an oven at 125° C. did not disperse in water. A sampleof the carbon black product that had been subjected to Soxhletextraction overnight with THF contained 1.57% phosphorous. Therefore,the carbon black product had 0.51 mmol/g of attached p-C₆H₄PO₃— groups.

Example 43 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example illustrates the use of a diazonium salt containing aquaternary ammonium salt in the preparation of a carbon black product ofthe present invention and the dispersibility in water of this carbonblack product. A cold solution of 3-amino-N-methylpyridinium nitrate (11mmol) in 30 g of water was added to a suspension of 11.0 g of a carbonblack (surface area 230, DBPA 70) in 70 g of water at <10° C.Concentrated HCl (2.38 g) was added. A cold solution of 0.92 g NaNO₂ in10 g water was added carefully, and the reaction mixture was stirred for20 minutes. The diazonium salt was formed in situ, and the salt reactedwith the carbon black. A solution of 0.50 g of NaOH in 10 g of water wassubsequently added. The sample was dried at 130° C., giving a carbonblack product. The carbon black product had a 325 mesh residue of 0.40%,compared to 94% for the untreated carbon black product.

Example 44 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example further illustrates the use of a diazonium salt containinga quaternary ammonium salt in the preparation of a carbon black productof the present invention and the dispersibility in water of this carbonblack product. Using a procedure analogous to that of Example 43 with9.8 mmol 4-(aminophenyl)-trimethylammonium nitrate, 10.0 g carbon black,2.25 g concentrated HCl, 0.83 g NaNO₂, a carbon black product with a 325mesh residue of 0.6% was obtained. The residue of the untreated carbonblack was 94%.

Example 45 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example shows that a carbon black product produced with anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g. Acold (5° C.) solution of 4-carboxymethyl-benzenediazonium chloride wasprepared from 0.77 g 4-aminophenylacetic acid, 9.2 g cold water, 1.35 gcold concentrated HCl and 0.44 g NaNO₂. The diazonium solution was addedto an ice cold stirring suspension of 5.04 g of the carbon black in 35.2g of water. Bubbles were released. After stirring for 20 minutes, thedispersion was placed in a water bath at 27° C. and stirred for anadditional 20 minutes. The dispersion was dried in an oven at 120° C.,leaving the carbon black product which had a 325 mesh residue of 2.5%,compared to 94% for the untreated carbon black.

Example 46 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

This example shows that a carbon black product with another diazoniumsalt was more readily dispersible in water than the correspondinguntreated carbon black. The carbon black used for treatment has asurface area of 230 m2/g and a DBPA of 70 ml/100 g. A pin pelletizer wascharged with 200 g of the carbon black. A suspension of 80 mmol (12.7 g)sodium 4-aminobenzoate in 45 g of water, 25.7 g concentrated HCl, and asolution of 7.04 g NaNO₂ in 30 g of water were added to the pelletizerin succession, with one minute of mixing after the first two additionsand five minutes after the last. Carboxybenzenediazonium chloride wasformed in situ and it reacted with the carbon black. A solution of 7.83g NaOH in 30 g water was added and mixing was continued for two minutes.The resulting carbon black product was dried at 120° C. and had a 325mesh residue of 6.4%, compared to 94% for the untreated carbon black.

Examples 47-59 Preparation of Carbon Black Products and their Use asColorants in ABS

These examples illustrate the preparation of carbon black products ofthe present invention using different amines and the use of these carbonblack products as colorants in ABS. A fluffy carbon black with a surfacearea of 230 m2/g and a DBPA of 70 ml/100 g was used in each example. Adiazonium salt was prepared in an ice bath from the compound indicated,2.2 equivalents of concentrated HCl, and 1.0 equivalents of NaNO₂ as a9.65M solution. The resulting solutions were added to a suspension of200 g of the fluffy carbon black in 3 L of water and stirred for 10 to20 minutes. The resulting carbon black product was filtered off, washedwith water twice, and dried at about 100° C. In some instances, thepreparation was carried out by combining multiple batches that had beenmade at one half or one quarter scale.

Masterbatches were prepared by fluxing 183 g ethylene-vinyl acetatepolymer (EVA) for one minute in a Brabender mixer at 110° C., adding45.8 g of the carbon black product, and mixing for four additionalminutes. Injection molded samples for evaluation were prepared byinjection molding a mixture of 80 g of masterbatch and 1520 g of ABS,(acrylonitrile-butadiene-styrene copolymer resin). The finalconcentration of the carbon black product in the molded samples is 1%.

The impact strength of the let down material was measured with an Izodimpact tester; the optical properties were measured with a Huntercalorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that the carbon black products of theinvention are useful as a colorant in ABS.

Impact Amount of strength, Diazonium % of Exam- Diazonium Precursor,unfilled Hun- Hun- Hun- ple Precursor mmol ABS ter L ter a ter b 47Aniline 60 84 6.4 −0.2 −1.3 48 4-Chloro- 60 87 6.6 −0.3 −1.5 aniline 494-Amino- 60 46 6.1 −0.3 −2.0 benzoic acid 50 Ethyl 4-amino 60 71 5.3−0.3 −1.6 benzoate 51 4-Nitro- 60 58 5.0 −0.3 −1.5 aniline 52 4-Hexyl-60 73 5.1 −0.3 −1.6 aniline 53 4-Tetradecyl- 60 66 5.7 −0.3 −1.7 aniline54 4-(N,N 60 48 5.7 −0.3 −1.7 Dimethyl amino)aniline 55 4-Amino 60 545.1 −0.3 −1.6 acetophenone 56 4-Amino 80 50 4.5 −0.2 −1.1 phenol 57p-Phenylene 60 45 5.2 −0.3 −1.6 diamine 58 p-Phenetidine 60 63 5.1 −0.3−1.6 59 Reference 53 5.0 −0.2 −1.6

Examples 60-62 Preparation of Carbon Black Products and their Use asColorants in ABS

These examples illustrate the preparation of carbon black products ofthe present invention using different treating agents and the use ofthose carbon black products as a colorant in ABS. A fluffy carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was used ineach case. The procedure for Examples 47-59 was used for the preparationof the carbon black products using 60 mmol of diazonium precursor.

Masterbatches were prepared by fluxing 203.6 g ABS for two minutes in aBrabender mixer with an initial temperature of 210° C., adding 50.9 g ofthe carbon black product at 175° C., and mixing for three additionalminutes. Injection molded samples for evaluation were prepared byinjection molding a mixture of 75 g of masterbatch and 1425 g of ABS.The final concentration of the carbon black product in the moldedsamples was 1%.

The impact strength of the let down material was measured with an Izodimpact tester; the optical properties were measured with a Huntercolorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that carbon black products of the inventionare useful as a colorant in ABS.

Impact Diazonium strength, % of Hunter Hunter Hunter Example Precursorunfilled ABS L a b 60 4-Aminophenol 32 4.5 −0.2 −1.1 61 p-Benzonitrile37 4.4 −0.1 −1.1 62 Reference 38 4.6 −0.2 −2.0

Examples 63-65 Preparation of Carbon Black Products and their Use inColoring Polyethylene

These examples illustrate the preparation of carbon black products ofthe present invention. A carbon black with a surface area of 140 m2/gand a DBPA of 114 ml/100 g was used. Cold solutions oftetradecylbenzenediazonium chloride were prepared fromtetradecylaniline, concentrated HCl, NaNO2, isopropanol and water. Thediazonium solution was added to 200 g carbon black in a pin pelletizerand mixed for the indicated time. Additional water #1 was added andmixing was continued for three more minutes. After addition of morewater #2 and isopropanol #2 and further mixing, the resulting carbonblack product was dried in an oven. A control sample was prepared bymixing the untreated carbon black in the same pelletizer with water andisopropanol, and drying.

Masterbatches were prepared by mixing 169.34 g low density polyethylenewith 72.6 g of a carbon black sample in a Brabender mixer at 85° C. forfive minutes. Plaques for evaluation were prepared by injection moldinga mixture of 10 g of masterbatch and 1490 g of high densitypolyethylene. The final concentration of carbon black product was 0.2%.The optical properties of the plaques were measured with a Huntercolorimeter. The results show that the carbon black products weresomewhat jetter (lower Hunter L values) than the control and are usefulas a colorant for polyethylene.

Example 63 Example 64 Example 65 Precursor 4-Tetra- 4-Tetra- nonedecylaniline decylaniline Precursor amount, g 6.95 11.56 — HCl, g 4.677.79 — H2O, g 27 48 — Isopropanol, g 25 25 — NaNO2, g 2.07 3.45 —Initial mix time, min 3 1 — Added water #1, g 170 130 — Added water #2,g 5 5 263 Added isopropanol #2, g — 5 20 Final mix time, min 1 2 5Hunter L 6.9 6.7 7.1 Hunter a −0.2 −0.3 −0.3 Hunter b 0.3 0.0 0.2

Example 66 Preparation of a Carbon Black Product in a Pelletizer

This example illustrates the preparation of a carbon black product ofthe present invention. A pelletizer was charged with 300 g of a carbonblack with a surface area of 254 m2/g and a DBPA of 188 m/100 g and 21.2g of sulfanilic acid. After mixing for 45 seconds, 220 g of water wasadded. After mixing for 20 seconds, 13.2 g of concentrated nitric acidwas added. After mixing for an additional 20 seconds, a solution of 10.3g of NaNO₂ in 270 g of water was added. After mixing for 2 minutes, theresulting carbon black product was dried in an oven at 125° C.

Example 67 Use of a Carbon Black Product in Polypropylene

This example illustrates the use of a carbon black product of thepresent invention in polypropylene to impart conductivity to thepolypropylene. A mixture of 263.1 g of the carbon black product ofExample 66 and 881 g of polypropylene was added to a Banbury mixer at66° C. and mixed for 5 minutes. A sample of the material was let down toa 20% carbon black product content on a two roll mill by mixing withadditional polypropylene. The product had a resistivity of 68 ohm-cm,compared to 64 ohm-cm for a similar product made with the untreatedcarbon black used in Example 66.

Examples 68-76 Preparation of Carbon Black Products

These examples show other diazonium compounds that can be used toprepare carbon black products of the present invention. The diazoniumcompounds encompass a range of substitution patterns on the aromaticring and with various electron-withdrawing or electron-donatingsubstituents. In each case, a cold diazonium salt solution was preparedfrom the indicated aryl amine, NaNO₂ and either concentrated HCl orHNO₃. The diazonium solution was added to a suspension of carbon blackin water and/or stirred for 15 to 20 minutes. The resulting carbon blackproduct was isolated by filtration, washed with water, and subjected toSoxhlet extraction with THF overnight. The analyses shown below reportincreases from the reaction over the level contained in the appropriateuntreated carbon black. The results show that a substantial fraction ofthe organic groups are attached to the carbon black product.

Carbon black Carbon black product product Treatment Cl N Fraction ofSubstituted Surface Area DBPA Level, Analysis Analysis bonded groupsphenyl groups Example Aryl amine m2/g ml/100 g μmol/g CB μmol/g μmol/gas % μmol/g 68 4-Chloro aniline 230 64 300 196 — 65 196 694-Chloro-3-methyl 230 64 300 215 — 72 215 aniline 70 4-Chloro-2-methyl230 64 300 170 — 57 170 aniline 71 4-Chloro-3-nitro 230 64 300 209 — 70209 aniline 72 4-Chloro-2-nitro 230 64 300 123 — 41 123 aniline 73Sodium 3 Amino 230 64 300 64 — 21 64 6-chloro benzene sulfonate 743-Amino Pyridine 350 *  120 580 — 461 79 461 75 4-Amino benzoni 230 70300 — 263 88 263 trile 76 4-Bromo-2-chloro 230 70 407 264 — 65 264aniline * CTAB Surface area

Example 77 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

This example illustrates the preparation of a carbon black productcontaining aryl and alkoxy groups. A dry sample of a carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used.Bromoethanol (30 ml) was added to a mixture of 3 g of the carbon blackand 0.34 g of dry chlorobenzenediazonium hexafluorophosphate. Bubbleswere released rapidly. After stirring for 30 minutes, the resultingcarbon black product was filtered, subjected to Soxhlet extractionovernight with THF and dried. The carbon black product contained 0.58%Cl and 0.84% Br compared to 0.02% Cl and <0.01% Br for the untreatedcarbon black product. The carbon black product therefore had 0.16 mmol/gof attached chlorophenyl groups and 0.11 mmol/g of attached bromoethoxygroups.

Example 78 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

This example illustrates the preparation of a carbon black productcontaining aryl and alkoxy groups. A dry sample of a carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used.Chloroethanol (30 ml) was added to a mixture of 3 g of the carbon blackand 0.32 g of dry bromobenzenediazonium tetrafluoroborate. Bubbles werereleased rapidly. After stirring for 30 minutes, the resulting carbonblack product was filtered, subjected to Soxhlet extraction overnightwith THF and dried. The carbon black product contained 0.31% Cl and1.60% Br compared to 0.02% Cl and 0.0 1% Br for the untreated carbonblack. The carbon black product therefore had 0.20 mmol/g of attachedbromophenyl groups and 0.08 mmol/g of attached chloroethoxy groups.

Example 79 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

This example illustrates another method for the preparation of a carbonblack product containing aryl and alkoxy groups. A carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used. A solutionof 4-bromobenzene diazonium nitrate was prepared in an ice bath from0.69 g bromoaniline, 0.33 g NaNO₂, 0.86 g concentrated HNO₃ and ca. 3 mlof water. The diazonium solution was added to a suspension of 10 gcarbon black product, 5 g chloroethanol and 85 g water that was stirringat room temperature. After stirring for 30 minutes, the carbon blackproduct was removed by filtration, washed with THF, and dried in an ovenat about 125° C. A sample that had been subjected to Soxhlet extractionovernight with THF contained 1.08% bromine and 0.16% chlorine. A controlcarbon black sample was prepared by stirring the same untreated carbonblack in a 5.6% chloroethanol/water solution, washing with THF, dryingand extracting with THF. The control contained 0.02% bromine and 0.082%chlorine. The carbon black product therefore had 0.13 mmol/g of attachedbromophenyl groups and 0.022 mmol/g of attached chloroethoxy groups.

Example 80 Preparation of a Carbon Black Product

This example further illustrates the preparation of a carbon blackproduct of the present invention. Concentrated HCl (16.2 g) was dilutedwith 40 g water and added to 9.30 g 4-aminophenyldisulfide. The mixturewas stirred in an ice bath. A cold solution of 6.21 g NaNO₂ in 30 gwater was added with stirring, keeping the mixture below 100° C.4-Diazophenyl disulfide dichloride is formed. The mixture was added to asuspension of 250 g of pelleted carbon black (iodine number of 120 mg/gand a DBPA of 125 ml/100 g) in 1.3 L of water at 10° C. with stirring.Bubbles were released. After stirring for 2½ hours, the product isfiltered, washed with ethanol, washed with additional water and thendried at 125° C. to a constant weight. A sample of the carbon blackproduct that was extracted overnight with THF and dried contained 1.75%sulfur, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.10 mmol/g of attached dithiodi-4,1-phenylenegroups.

Example 81 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. Concentrated HCl (5.4 g) was diluted with 40 gwater and added to 3.1 g 4-aminophenyldisulfide. The mixture was stirredin an ice bath, and 50 g additional cold water was added. A coldsolution of 2.07 g NaNO₂ in 30 g water was added with stirring, keepingthe mixture below 10° C. 4-Diazophenyl disulfide dichloride was formed.The mixture was added to a suspension of 125 g of pelleted carbon black(iodine number of 120 mg/g and a DBPA of 125 ml/100 g) in about 800 g ofwater at 10-15° C. with stirring. Bubbles were released. After stirringfor 2 hours, the resulting carbon black product was filtered, washedwith ethanol, washed with additional water and then dried at 125° C. toa constant weight. A sample of the carbon black product that wasextracted overnight with THF and dried contained 1.56% sulfur, comparedto 1.08% for the untreated carbon black. Therefore, the carbon blackproduct had 0.075 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 82 Preparation of a Carbon Black Product

This example further illustrates the preparation of a carbon blackproduct of the present invention. A pelleted carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 ml/100 g was used. Butyl lithium(50 mL of a 1.0 M solution in hexane) was added to 200 mL of dry DMSOunder nitrogen. A solution of 11.1 g of 4-aminophenyl disulfide in 100mL dry DMSO was prepared and added under nitrogen with cooling from anice bath. A dark violet colored developed. S₂Cl₂ (3.3 mL) was added over10 minutes with stirring and continued cooling. A solution of 1.7 g NaOHin water was added. After addition of more water, the product wasextracted with 450 mL of ether. The ether was removed under vacuum, andthe residue was dissolved in CH₂Cl₂, washed with water, dried andconcentrated under vacuum to give 4-aminophenyltetrasulfide as an oil.

4-Aminophenyl tetrasulfide (5.85 g) was stirred with 150 g of water inan ice bath. A cold solution of 8.1 g concentrated HCl in 50 g water wasadded, followed gradually by a solution of 3.2 g NaNO₂ in 40 g water,forming 4-diazophenyl tetrasulfide dichloride. After stirring, theresulting suspension was added to a stirring slurry of 125 g of thepelleted carbon black in about 800 g of water. Bubbles were released.After stirring for 2½ hours, the resulting carbon black product wasfiltered off, washed with ethanol, washed with water and dried at 140°C. A sample of the carbon black product that had been extracted with THFovernight and dried contained 1.97% sulfur, compared to 1.08% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached tetrathiodi-4,1-phenylene groups.

Example 83 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 120 mg/gand a DBPA of 125 ml/100 g was used. A cold solution of 2.65 gconcentrated HCl and 30 g water was added to a mixture of 2.85 g4-aminophenyl phenyl disulfide in 50 g water that was stirring in an icebath. A cold solution of 1.04 g NaNO₂ in 30 g of water was added over aperiod of 10 minutes. 4-Diazophenyl phenyl disulfide chloride wasformed. The diazonium suspension was added to a suspension of 122 gcarbon black in about 800 g water that was stirring at 15° C. Bubbleswere released. After stirring for about two hours, the carbon blackproduct was filtered off, washed with isopropanol, washed with water,and dried in an oven at about 125° C. A sample of the carbon blackproduct that had been subjected to Soxhlet extraction overnight with THFand dried had a sulfur content of 1.32%, compared to 1.08% for theuntreated carbon black. Therefore, the carbon black product had 0.038mmol/g of attached phenyldithiophenylene groups.

Example 84 Preparation of a Carbon Black Product

This example further illustrates the preparation of a carbon blackproduct of the present invention. Nitrogen dioxide (4.1 g) was bubbledinto 40 g water that was cooled in an ice bath. The resulting solutionwas added slowly to a cold (10° C.), stirring suspension of 4.65 g of4-aminophenyl disulfide in 100 g water. The resulting solution of4-diazophenyl disulfide dinitrate was added to a cold stirringsuspension of 125 g of carbon black (iodine number of 120 mg/g and aDBPA of 125 ml/100 g) in 800 g cold (12-14° C.) water. The reactionmixture was stirred for 3 days, and allowed to warm to room temperaturein the process. The resulting carbon black product was recovered byfiltration and was dried. A sample of the carbon black product extractedwith THF overnight had 1.81% sulfur, compared to 1.07% sulfur in theuntreated carbon black product. Therefore, the carbon black product had0.12 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 85 Preparation of a Carbon Black Product

This example further illustrates the preparation of a carbon blackproduct of the present invention. The procedure of Example 80 wasfollowed, except that a carbon black with an iodine number of 90 mg/gand a DBPA of 114 ml/100 g was used, and except that an additional 50 mlof water was used to form the aminophenyl disulfide dihydrochloridesuspension. A sample of the resulting carbon black product that had beenextracted overnight with THF and dried contained 2.12% sulfur, comparedto 1.45% for the untreated carbon black. Therefore, the carbon blackproduct had 0.10 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 86 Preparation of a Carbon Black Product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 120 mg/gand a DBPA of 125 ml/100 g was used. A cold solution of4-diazo-2-chlorophenyl disulfide dichloride was prepared by adding acold solution of 3.59 g of NaNO₂ in 40 g water to a suspension of 6.6 g4-amino-2-chlorophenyl disulfide, 9.12 g concentrated HCl and about 150g water that was stirring in an ice bath. After stirring for fiveminutes, the diazonium solution was then added to a stirred suspensionof 140 g of carbon black in 1 liter of water at 10-14° C. After stirringfor two hours, the resulting carbon black product was filtered off,washed with ethanol, washed with water, and then dried in an oven at125° C. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a sulfur content of1.60%, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.081 mmol/g of attacheddithiodi-4,1-(3-chlorophenylene) groups.

Example 87 Preparation of a Carbon Black Product with a Diazonium SaltGenerated In Situ

This example illustrates the preparation of a carbon black product ofthe present invention with a diazonium salt that is generated in situ. Acarbon black with an iodine number of 120 mg/g and a DBPA of 125 ml/100g was used. 4-Aminophenyl disulfide (8.38 g) was dissolved in a solutionof 14.65 g of concentrated HCl and about 150 g of water, and added to astirred slurry of 225 g of carbon black in about 1.4 L of water. Asolution of 5.28 g NaNO₂ in about 50 g water was added, forming4-diazophenyl disulfide in situ, which reacted with the carbon black.After stirring for two hours, the resulting carbon black product wasremoved by filtration, washed with ethanol, washed with water, and driedat about 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction overnight with THF and dried contained1.89% sulfur, compared against 1.08% for the untreated carbon black.Therefore, the carbon black product had 0.13 mmol/g of attacheddithiodi-4,1-phenylene groups.

Example 88 Preparation of a Carbon Black Product

A carbon black product having attached dithiodi-4,1-phenylene groups wasprepared by following the method of Example 80 and using a suspension of8.38 g 4-aminophenyl disulfide in about 100 g of water, a solution of13.65 g concentrated HCl in 40 g of water, a solution of 5.04 g NaNO₂ in30 g of water, and a slurry of 225 g of the same carbon black in 1.4 Lof water. The carbon black slurry was stirred at 10-14° C. when thediazonium solution was added.

Examples 89 and 90 Comparative Carbon Black Products

In these comparative examples, the carbon blacks used in Examples 80 and85 were washed with water, ethanol and water, and subsequently dried togive the comparative carbon black products of Examples 88 and 89,respectively.

Examples 91-99 Use of Different Carbon Blacks for the Preparation ofCarbon Black Products that are Water Dispersible

This example shows the use of a variety of carbon blacks in thepreparation of carbon black products of the present invention. Thisexample also shows that the carbon black products were more readilydispersible in water than the corresponding unreacted carbon blacks.Sulfanilic acid was dissolved in 200 g of hot water. The carbon blackproduct (30 g) was added and the mixture was allowed to cool to 25 to30° C. Concentrated HCl was added (2.15 equivalents based on thesulfanilic acid used) and then a 9.65M solution of NaNO₂ in water wasadded (1.2 equivalents based on the sulfanilic acid used), forming4-sulfobenzenediazonium hydroxide in situ, which reacted with the carbonblack. After stirring for 30 minutes, the resulting dispersion was driedin an oven at 100° C., giving the resulting carbon black product.

Original Original Residue of Carbon Black Carbon black Residue of auntreated Surface Area product DBPA Sulfanilic carbon black carbon blackExample m2/g ml/100 g acid g product, % product, % 91 350 ** 120 6.981.0 97 92 140 114 3.03  0.6* 45 93 1500 330 32.55  0.6* 35 94 42 1210.91 0.1 26 95 80 85 1.73 <0.1   81 96 24 132 0.44 4.6 31 97 24 132 1.500.2 31 98 254 178 5.43 <0.1   23 99 18 39 0.93 4.4 40 *Filtered througha 20 micron filter. ** CTAB surface area

Example 100 Preparation of a Carbon Black Product and its Use in thePreparation of Black Paper

This example shows the preparation of a carbon black product of thepresent invention and the use of that product in the preparation ofblack paper. A carbon black (300 g) with a surface area of 80 m2/g and aDBPA of 85 ml/100 g was added to a pin pelletizer with 18.2 g ofsulfanilic acid. After mixing briefly, 150 g of water, 11.2 g ofconcentrated nitric acid, 30 g of water and a solution of 8.78 g ofNaNO2 in 35 g of water were added in succession with 15 seconds ofmixing after each addition. 4-Sulfobenzenediazonium hydroxide inner saltwas formed in situ and it reacted with the carbon black. The resultingcarbon black product was dried in an oven at 125° C. A dispersion ofthis carbon black product was prepared by dispersing it in water in alaboratory homogenizer for 30 seconds.

A comparative dispersion was made by grinding 200 g of the sameunreacted carbon black in a solution of 7 g of a lignosulfonatedipsersant, 5 ml concentrated NH₄OH and 770 g water with grinding mediain a ball mill for 4 hours, at which point a Hegman gauge reading of 7was obtained.

Penobscott bleached hardwood kraft pulp (160 g) and St. Felicianbleached softwood kraft pulp (240 g) were dispersed in water in a Cowlesdissolver. The stock solution was transferred into a TAPPI standardlaboratory beater and diluted to a volume of 23 liters. The stocksolution was circulated in the beater for five minutes, and then placedunder load and beaten for 50 minutes to a corrected Canadian StandardFreeness of 355 ml.

Sufficient pulp to make three 2.75 g hand sheets was diluted to 3 L, andthe appropriate amount of carbon black dispersion was incorporated. Asuspension was prepared for each carbon black loading level. Eachsuspension was divided into three portions. The first portion was usedas is. Rosin and alum were added to the second portion at the rates of80 pounds and 60 pounds per bone dry ton, respectively. HERCON 79 (AKD)size and BL 535 retention aid were added to the third portion at therates of four pounds and three pounds per bone dry ton, respectively.One 8″×8″ Noble & Wood handsheet was made from each sample. Theresulting handsheets were evaluated for TAPPI brightness using 45°/0°geometry.

HERCON is a registered trademark for sizes produced and sold by HerculesInc., Wilmington Del. BL 535 is available from Buckman Laboratories,Inc., Memphis Tenn.

The following table shows the brightness of handsheets made with thecarbon black product dispersion and with the control dispersion. Thesedata show that the carbon black product can be used to color paper.These data also show that when the paper was made with an acidic rosinsize and an alum retention aid, the carbon black product was retainedmore efficiently and advantageously at low loading levels when comparedagainst the unreacted carbon black. These data further show that whenthe paper was made with an alkaline AKD size and BL 535 retention aid,the carbon black product was retained more efficiently andadvantageously at low loading levels when compared against the unreactedcarbon black.

Carbon black Brightness, Brightness, product, Treated Untreated poundsper carbon black carbon black bone dry ton None AKD Alum product product10 X 67 69 46 50 15 X 67 67 43 50 25 X 59 61 34 41 50 X 44 47 18 24 100X 33 36 9 13 200 X 20 23 0 5 10 X 16 18 21 23 15 X 12 13 19 21 25 X 1113 14 16 50 X 7 8 10 11 100 X 7 7 7 8 200 X 4 5 5 5 10 X 16 20 22 24 15X 13 16 19 21 25 X 11 12 13 14 50 X 8 10 9 11 100 X 7 9 6 7 200 X 6 8 45

Example 101 Use of a Carbon Black Product in the Preparation of anAqueous Ink

This example illustrates the advantages of using a carbon black productof the present invention in an aqueous ink formulation. Ink compositionA was prepared by adding 3.13 parts of the carbon black product ofExample 13 to a vehicle made by mixing 2.92 parts JONCRYL 61LV resin,0.21 parts isopropanol, 0.31 parts ARROWFLEX defoamer, 7.29 partsJONCRYL 89 resin and 6.98 parts water, and shaking the composition for10 minutes on a paint shaker. The table below shows the 635 mesh residuelevel.

JONCRYL is a registered trademark for resins produced and sold by SCJohnson Polymer, Racine, Wis. ARROWFLEX is a registered trademark fordefoamers produced and sold by Witco, New York, N.Y.

Ink composition B was prepared by grinding a mixture of 120 parts of thecarbon black product used in Example 13, 112 parts of JONCRYL 61LVresin, 8 parts of isopropanol, 4 parts of ARROWFLEX defoamer, 156 partsof water and 400 g of grinding media. In order to check the grind level,samples were periodically let down to composition C that contained 15.0parts carbon black product, 14.0 parts JONCRYL 61LV resin, 1.0 partsisopropanol, 1.7 parts ARROWFLEX DEFOAMER, 35.1 parts Joncryl 89 and33.4 parts water.

Ink composition D was prepared by grinding a mixture of 120 parts of theuntreated carbon black used in Example 13, 112 parts of JONCRYL 61LV,resin, 8 parts of isopropanol, 4 parts of ARROWFELX defoamer, 156 partsof water and 400 g of grinding media. In order to check the grind level,samples were periodically let down to composition E that contained 15.0parts carbon black product, 14.0 parts JONCRYL 61LV resin, 1.0 partsisopropanol, 1.7 parts ARROWFLEX defoamer, 35.1 parts JONCRYL 89 resinand 33.4 parts water.

The residues from ink compositions A, C and E as a function of grindingtime are provided in the following table, and clearly show that a carbonblack product of the present invention disperses more readily than thecorresponding unreacted carbon black in these aqueous inks.

Ink A Ink C Ink E 635 Mesh 635 Mesh 635 Mesh Dispersion time Residue, %Residue, % Residue, % 10 Minutes shaking 2.6 — — 20 Minutes Ball Mill —0.3 — 40 Minutes Ball Mill — 0.2 — 1 Hour Ball Mill — 0.02 about 100 2Hours Ball Mill — — 10.8 3 Hours Ball Mill — — 5.8 4 Hours Ball Mill — —0.9 10 Hours Ball Mill — — 0.5 14 Hours Ball Mill — — 0.3 15 Hours BallMill — — 1.0 16 Hours Ball Mill — — 1.0

Example 102 Use of a Carbon Black Product in the Preparation of anAqueous Coating

This example shows that carbon black products of the present inventionare useful for the preparation of aqueous coatings. The carbon blackproduct from Example 9 (10 g) was dispersed in 90 g of water by stirringfor 10 minutes. Coating composition A was prepared by stirring 4.3 g ofthis dispersion into a mixture of 7.53 g of CARGILL 17-7240 acrylicresin, 0.80 g of dimethylethanolamine (DMEA), 19.57 g water, 0.37 gSURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347 melamine resin, 0.53 gethylene glycol monobutyl ether and 0.075 g BYK-306 surfactant. CARGILL17-7240 acrylic resin and CARGILL 23-2347 melamine resin are availablefrom Cargill Inc., Minneapolis, Minn. SURFYNOL CT136 is a registeredtrademark for surfactants produced and sold by Air Products andChemicals, Inc., Allentown, Pa. BYK-306 is a registered trademark forsurfactants produced and sold by BYK-Chemie USA, Wallingford.

A millbase was prepared by grinding an oxidized carbon black product (15g) with a surface area of 560 m2/g, a DBPA of 80 ml/100 g and a volatilecontent of 9% in a mixture of 74.6 g of CARGILL 17-7240 acrylic resin,9.53 g DMEA, 236.5 g water and 16.35 g CT-136 surfactant until its meanvolume particle size was 0.18 microns. Comparative coating composition Bwas prepared by mixing 24.4 g of this millbase with a mixture of 17.51 gCARGILL 17-7240 acrylic resin, 1.74 g DMEA, 50.56 g water, 3.97 gCARGILL 23-2347 melamine resin, 1.59 g ethylene glycol monobutyl etherand 0.23 g BYK-306 surfactant. Glossy lenetta paper coated withcompositions A and B was dried at 350° F. for 10 minutes. A clear coatwas applied, and the samples were dried again. The paper coated withcomposition A had Hunter L,a,b values of 1.0, 0.01 and 0.03,respectively, compared to 1.1, 0.01 and −0.06, respectively for thepaper coated with comparative composition B.

Example 103 Preparation of a Carbon Black Product and its Use in anAqueous Coating

This example illustrates the preparation of a carbon black product ofthe present invention and the use of this carbon black product in anaqueous coating. A carbon black (200 g) with a CTAB surface area of 350m2/g and a DBPA of 120 ml/100 g was added to a stirred solution of 42.4g sulfanilic acid in 2800 g of water. Nitrogen dioxide (25.5 g) wasdissolved in 100 g of cold water and added to the carbon black productsuspension. Bubbles were released. 4-Sulfobenzenediazonium hydroxideinner salt was formed in situ, which reacted with the carbon black.After stirring for one hour, 5 g of additional NO₂ was added directly tothe carbon black dispersion. The dispersion was stirred for anadditional 15 minutes, and left overnight. The resulting carbon blackproduct was recovered by drying the dispersion in an oven at 130° C.

A dispersion of this carbon black product was prepared by stirring 10 gof the carbon black product in 90 g of water. Coating composition C wasprepared by stirring 4.3 g of this dispersion into a mixture of 7;53 gof CARGILL 17-7240 acrylic resin, 0.80 g of DMEA, 19.57 g water, 0.37 gSURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347 melamine resin, 0.53 gethylene glycol monobutyl ether and 0.075 g BYK-306 surfactant.

A millbase was prepared by grinding (in an attritor) an oxidized carbonblack product (15 g) with a surface area of 560 m2/g, a DBPA of 91ml/100 g and a volatile content of 9.5% in a mixture of 74.6 g ofCARGILL 17-7240 acrylic resin, 9.53 g DMEA, 236.5 g water and 16.35 gSURFYNOL CT-136 surfactant for 24 hours. Comparative coating compositionD was prepared by mixing 24.4 g of this millbase with a mixture of 17.51g CARGILL 17-7240 acrylic resin, 1.74 g DMEA, 50.56 g water, 3.97 gCARGILL 23-2347 melamine resin, 1.59 g ethylene glycol monobutyl etherand 0.23 g BYK-306 surfactant.

Glossy lenetta paper coated with compositions A and B was dried at 350°F. for 10 minutes. A clear coat was applied, and the samples were driedagain. The paper coated with composition C had Hunter L, a, and b valuesof 1.0, 0.01 and 0.03, respectively, compared to 1.1, 0.01 and −0.06,respectively for the paper coated with comparative composition D.

Examples 104-108 Use of Carbon Black Products in Rubber Formulations

This example illustrates the use of the carbon black products ofexamples 80 to 84 and the comparative example 89 in rubber formulations.The polymer is milled in a Brabender mixer for 1 minute at 100° C. Amixture of ZnO and the carbon black product was added and mixed for 2additional minutes. The stearic acid and FLEXZONE 7P anti-degradant wereadded and mixed for 2 additional minutes. The sample was dumped, cooledand mixed at 80° C. for 1 minute, the curatives were added, and themixing was continued for an additional minute. The sample was thenpassed through a two roll mill three times. The recipes and performancedata in each case are given in the tables below. NS 114 is a chemicallymodified tin coupled solution SBR available from Nippon Zeon, Japan.FLEXZONE is a registered trademark for antidegradant products availablefrom Uniroyal Chemical, Naugatuck, Conn.

Compara- Example 104 105 106 107 108 tive NS 114 100 100 100 100 100 100CB Product 50 Example 80 CB Product 50 Example 81 CB Product 50 Example82 CB Product 50 Example 83 CB Product 50 Example 84 Control CB 50Example 89 ZnO 3 3 3 3 3 3 Stearic Acid 2 2 2 2 2 2 FLEXZONE 1 1 1 1 1 17P product CBS * 1.25 1.25 1.25 1.25 1.25 1.25 MBT ** 0.2 0.2 0.2 0.20.2 0.2 Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 Total 159.2 159.2 159.2159.2 159.2 159.2 * CBS = cyclohexylbenzothiazylsulfenamide ** MBT =mercaptobenzothiazole

100% 300% Bound Abrader Abrader Modulus Modulus Tensile Elong. Hardnessrubber Tan δ Tan δ index index Mpa Mpa Mpa % Shore A % 0° C. 70° C. 14%slip 21% slip Example 104 4.18 — 19.5 290 60 44.5 0.244 0.114 122 142Example 105 3.93 — 16.7 274 60 39.6 0.265 0.137 114 141 Example 106 4.3319.1 20.9 314 61 35.2 0.277 0.131 110 132 Example 107 3.44 15.2 19.6 37261 30.8 0.304 0.170 103 105 Example 108 3.67 17.6 19.6 335 60 40.9 0.2510.122 113 129 Comparative 3.25 14.1 18.4 385 60 28.1 0.327 0.173 100 100

These data show that carbon black products of the present invention areuseful in rubber formulations. They further show that significantincreases in modulus, bound rubber and abrasion resistance are obtained,as are significant decreases in Tan δ. The magnitude of the effectdepends on the treatment level as well as on the specific groupsattached to the carbon black product.

Examples 109-112 Use of a Carbon Black Product in Rubber Formulations

This example illustrates the use of a carbon black product of thepresent invention in several different rubber formulations. Rubbercompounds were prepared from the carbon black product of Example 85 andof the comparative carbon black product of Example 90 by the methoddescribed for examples 104-108 using the recipes below. DURADENE 715 isa solution SBR. DURADENE is a registered trademark for SBR productsavailable from Firestone, Akron Ohio.

Example 109 Comparative 110 Comparative 111 Comparative 112 ComparativeSBR 1500 100 100 Duradene715 100 100 50 50 NR 100 100 50 50 CB Product50 50 50 50 Example 85 Control CB 50 50 50 50 Example 90 ZnO 3 3 3 3 4 43 3 Stearic Acid 2 2 2 2 2 2 2 2 Flexzone 7P 1 1 1 1 1 1 1 1 CBS 1.251.25 1.25 1 1 1 1.25 1.25 MBT 0.2 0.2 0.2 0.2 Sulfur 1.75 1.75 1.75 1.751.5 1.5 1.5 1.5 Total 159.2 159.2 159.2 159.2 159.5 159.5 158.75 158.75

The performance data in the table below show that carbon black productsaccording to the invention are useful in several different rubberformulations.

100% 300% Bound Abrader Abrader Modulus Modulus Tensile Elong. Hardnessrubber Tan δ Tan δ index index Mpa Mpa Mpa % Shore A % 0 C. 70 C. 14%slip 21% slip Example 109 4.12 19.3 21.9 338 60 29.8 0.241 0.155 84 117Comparative 3.70 17.3 23.0 393 62 28.0 0.280 0.182 100 100 Example 1104.79 — 14.4 233 63 32.4 0.477 0.146 81 175 Comparative 4.10 — 16.3 28261 28.6 0.544 0.173 100 100 Example 111 3.32 15.1 24.4 456 55 39.1 0.2210.142 98 135 Comparative 3.48 17.1 27.3 468 57 43.6 0.240 0.138 100 100Example 112 3.77 15.7 19.0 358 58 33.3 0.296 0.156 100 176 Comparative3.39 15.4 23.3 441 58 35.1 0.335 0.175 100 100

Example 113 Use of Treated Carbon Black in a Rubber Formulation

This example illustrates the use of a treated carbon black of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the treated carbon black of example 86 and the comparativecarbon black of example 89 by the method described in examples 104-108.The formulations and performance data are shown in the following tables.These results show that the treated carbon black is useful in thisrubber formulation. NS 116 is a chemically modified tin coupled solutionSBR and is available from Nippon Zeon, Japan.

Example 113 Comparative NS 116 100 100 CB Product Example 86 50 ControlCB Example 89 50 ZnO 3 3 Stearic Acid 2 2 FLEXZONE 7P product 1 1 CBS1.25 1.25 MBT 0.2 0.2 Sulfur 1.75 1.75 Total 159.2 159.2 100% 300% BoundAbrader Abrader Modulus Modulus Tensile Elong. Hardness rubber Tan δ Tanδ index index Mpa Mpa Mpa % Shore A % 0 C. 70 C. 14% slip 21% slipExample 113 4.46 17.3 18.3 316 64 28.0 0.787 0.190 72 110 Comparative4.12 16.7 21.2 367 63 26.2 0.818 0.219 100 100

Example 114 Use of a Carbon Black Product in a Rubber Formulation

This example illustrates the use of a carbon black product of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the carbon black product of Example 87 and the comparativecarbon black of Example 89 by the method described in Examples 104-108.The formulations and performance data are shown in the following tables.These results show that the carbon black product is useful in thisrubber formulation.

Example 114 Comparative NS 116 100 100 CB Product Example 87 50 ControlCB Example 89 50 ZnO 3 3 Stearic Acid 2 2 FLEXZONE 7P product 1 1 CBS1.25 1.25 MBT 0.2 0.2 Sulfur 1.75 1.75 Total 159.2 159.2 100% 300% BoundAbrader Abrader Modulus Modulus Tensile Elong. Hardness rubber Tan δ Tanδ index index Mpa Mpa Mpa % Shore A % 0 C. 70 C. 14% slip 21% slipExample 114 5.04 — 16.6 242 60 39.0 0.816 0.145 88 137 Comparative 4.1216.7 21.2 367 63 26.2 0.818 0.219 100 100

Examples 115-116 Use of Carbon Black Product in Rubber Formulations

These examples illustrate the use of a carbon black product of thepresent invention in two rubber formulations that are peroxide cured.Rubber compounds were prepared from the carbon black product of Example88 and from an untreated comparative carbon black with an iodine numberof 120 mg/g and a DBPA of 125 ml/100 g. The method described in Examples104-108 was used with the recipies below.

Example 115 Comparative 116 Comparative NS-114 100 100 Duradene 715 100100 CB Product 50 50 Example 88 Control CB 50 50 ZnO 3 3 3 3 StearicAcid 2 2 2 2 Flexzone 7P 1 1 1 1 Dicumyl peroxide 2 2 2 2 Total 158 158158 158

The performance data in the table below show that this carbon blackproduct is useful in rubber formulations using a peroxide cure.

100% 200% Bound Abrader Abrader Modulus Modulus Tensile Elong. Hardnessrubber Tan δ Tan δ index index Mpa Mpa Mpa % Shore A % ° C. 70° C. 14%slip 21% slip Example 115 3.66 10.4 23.9 356 61 3.3 0.208 0.119 98 101Comparative 2.94 8.1 21.8 398 62 18 0.284 0.156 100 100 Example 116 5.1111.5 13.9 233 67 17.5 0.299 0.152 65 74 Comparative 4.07 11.3 20.3 32161 22.1 0.343 0.180 100 100

Example 117 Use of a Carbon Black Product to Color Textiles

This example illustrates the use of a carbon black of the presentinvention to color textiles. Samples of textiles were placed for thetime indicated below in a stirring dispersion of the carbon blackproduct of Example 16 having attached C₆H₄SO₃— groups at the indicatedconcentrations at 100° C. The pH was adjusted as shown. The samples wereremoved, allowed to drain briefly, and posttreated by placing for about30 seconds in hot water, a hot 1 M solution of NaCl or a hot 0.015 Msolution of Al₂(SO₄)₃. When the pH of the carbon dispersion wasadjusted, the pH of the NaCl and Al₂(SO₄)₃ posttreatment solutions wereadjusted to match. The samples were then washed with water and dried.The L values below show that the textiles were effectively colored withthe carbon black product. Lower L values represent darker materials.

Carbon conc. Time Post treatment Hunter Textile M pH Min. H2O NaCl Al2(SO4)3 L Cotton 0.1 A 15 X 34.1 Cotton 0.1 A 45 X 33.6 Cotton 0.1 A 45 X30.3 Cotton 0.1 A 45 X 29.1 Cotton 0.01 A 45 X 67.4 Linen 0.1 A 45 X43.2 Linen 0.1 A 45 X 37.3 Linen 0.1 A 45 X 37.8 Wool 0.1 3.5 15 X 22.2Wool 0.1 3.5 45 X 18.6 Wool 0.1 3.5 45 X 20.0 Wool 0.1 3.5 45 X 17.8Wool 0.1 5.5 45 X 28.0 Silk 0.1 5.5 15 X 34.9 Silk 0.1 5.5 45 X 34.9Silk 0.1 5.5 45 X 41.4 Silk 0.1 5.5 45 X 22.2 Polyester 0.1 A 45 X 45.1Nylon 0.1 3.5 15 X 41.6 Nylon 0.1 3.5 45 X 35.3 Nylon 0.1 3.5 45 X 35.4Nylon 0.1 3.5 45 X 27.8 Nylon 0.1 5.5 45 X 34.8 A: pH not adjusted

Carbon Black Products Example 118

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/00 g was used.

4-aminophenyl-2-benzothiazolyl disulfide was prepared according to themethod described in Brzezinska, E.; Ternay, Jr., A. L. J. Org. Chem.1994, vol. 59, pp. 8239-8244. 4-aminophenyl-2-benzothiazolyl disulfide(9.79 g) was dissolved in 300 mL of ethanol at 75° C. and added to astirred slurry containing 225 g of carbon black pellets in 1 liter ofethanol and 6.37 g of 70% nitric acid. To the resulting slurry was addeda 10 mL solution of NaNO₂ (2.64 g). Gas was evolved. After stirring for48 hours most of the ethanol had evaporated and the resulting carbonblack product was collected washed with water and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.77% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆H₄)—S—S-(2-C₇H₅NS) groups.

Example 119

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-2-benzothiazolyl disulfide (14.1 g) was prepared as inExample 118 and was dissolved in a solution consisting of 10.1 g of 37%HCl, 360 mL of water and 560 mL of acetone. The orange solution was thenadded to a stirred slurry of carbon black pellets in 0.8 liters of waterand 1.2 liters of acetone. A solution of NaNO₂ (3.81 g) in 60 mL ofwater and 90 mL of acetone was added to the slurry in one portion. Gaswas evolved. The slurry was stirred overnight and filtered to collectthe carbon black product. The carbon black product was washed withwater, collected by filtration and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.77% sulfur, compared to 1.09% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆H₄)—S—S-(2-C₇H₅NS) groups.

Example 120

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-4′-hydroxyphenyl disulfide was prepared as follows.4-aminophenyl-2-benzothiazolyl disulfide (14.5 g) was dissolved in 325mL of chloroform yielding an orange solution. Over the course of 30minutes a solution of 4-hydroxythiophenol (6.78 g) in 60 mL ofchloroform was added dropwise. After addition was complete, the reactionmixture was stirred overnight. The chloroform solution was extracted ina separatory funnel with a solution of 5.3 g of 37% HCl diluted in 200mL of water. The aqueous layer was collected, neutralized with 5% NaOH,and extracted with ethyl acetate. The ethyl acetate layer was isolated,dried over MgSO₄ and filtered. Removal of the ethyl acetate gave 10.5 gof 4-aminophenyl-4′-hydroxyphenyl disulfide as a yellow oil.

To a stirred slurry of 4-aminophenyl-4′-hydroxyphenyl disulfide (8.13g), prepared as described above, in 300 mL of water was added a solutionof 6.99 g of 37% HCl in 75 mL of water. The resulting white suspensionwas added to a slurry of 225 g of carbon black pellets in 1.5 liters ofwater and the mixture stirred for 5 minutes. A solution of NaNO₂ (2.64g) in 100 mL of water was added to the slurry. Gas was evolved. Afterstirring the slurry overnight, the carbon black product was isolated byfiltration and washed with water. The carbon black product was thendried at 125° C. to constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.67% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)—OH groups.

Example 121

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of 237 g of carbon black pellets in 1.4 liters ofwater was added a solution of 4.44 g of 4-aminothiophenol and 7.36 g of37% HCl in 250 mL of water. To the resulting slurry was added a solutionof NaNO₂ (2.78 g) in 75 mL of water. Gas was evolved. The slurry wasstirred for 2.5 hours, filtered, and washed with water. The carbon blackproduct was then dried at 125° C. to constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.63% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.15 mmol/g ofattached -(4-C₆H₄)—SH groups.

Example 122

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of 6-amino-2-mercaptobenzothiazole (6.14 g) in 300mL of water was added 6.99 g of 37% HCl in 75 mL of water. The resultingslurry was cooled to 10° C., and a similarly cooled solution of NaNO₂(2.64 g) in 50 mL of water was added. The resulting orange slurry wasstirred for 30 seconds then added to a stirred slurry of 225 g of carbonblack pellets in 1.4 liters of water and 300 g of ice. Gas was evolved.The slurry was stirred for 2.5 hours and then filtered. The carbon blackproduct was then washed with water and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.98% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.135 mmol/g ofattached -6-(2-C₇H₄NS)—SH groups.

Example 123

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis[2-(4-aminophenyl)ethyl]disulfide was prepared as follows. To arefluxing solution of 4-nitrophenylethylbromide (23 g) in a mixture of280 mL of methanol and 70 mL of water was added a solution ofNa₂S₂O₃•5H₂O (31 g) in 75 mL of water. A further 60 mL of water was thenadded to the reaction mixture. Refluxing conditions were continued for 5hours. The resulting pale yellow solution was allowed to cool to roomtemperature. Methanol was removed from the solution on a rotaryevaporator leaving a white crystalline aqueous slurry. Addition of 300mL of water to the slurry yielded a slightly cloudy solution. To thisaqueous solution of sodium 4-nitrophenylethylthiosulfate was added asolution of Na₂S•9H₂O (120 g) in 300 mL of water. The reaction mixturerapidly grew cloudy and slightly yellow and, after several minutes ofstirring, a white precipitate formed. This slurry was heated to refluxfor 18 hours then cooled. An orange oil was present which was extractedwith several portions of ethyl acetate. The ethyl acetate extracts werecombined, dried over MgSO₄, and filtered. Removal of the ethyl acetateyielded 12 g of bis[2-(4-aminophenyl)ethyl]disulfide as an orange oil.

To a stirred slurry of bis[2-(4-aminophenyl)ethyl]disulfide (5.02 g),prepared as described above, in 200 mL of water was added a solution of6.67 g of 37% HCl in 100 mL of water. After stirring for 20 minutes anorange solution was obtained and was added to a stirred slurry of carbonblack pellets in 1 liter of water. To the resulting slurry was added asolution of NaNO₂ (2.46 g) in 100 mL of water. Gas was evolved. Afterstirring the slurry overnight, the carbon black product was filtered,washed with water, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.81% sulfur, compared to 11.11% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆H₄)—CH₂CH₂—S—S—CH₂CH₂-(4-C₆H₄)— groups.

Example 124

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis[2-(4-aminophenyl)ethyl]trisulfide was prepared as follows. To aslurry of iron powder (28.4 g) in 300 mL of water at 100° C. in a 500 mLErlenmeyer flask was added 1.42 g of FeSO₄•7H₂O.4-nitrophenylethylthiosulfate (29 g), prepared according to theprocedure outlined in Example 123, was added to the iron slurry in 1gram portions over the course of 5 minutes while maintaining atemperature of 96-98° C. During the addition, the flask was manuallyshaken to ensure good mixing. After the addition of4-nitrophenylethylthiosulfate was complete, a further 9.5 g of Fe wasadded and heating continued for 5 minutes. Once the flask had cooled toroom temperature, several drops of conc. NH₄OH were added to adjust thepH of the reaction mixture from 5 to 9.5. The mixture was then filteredand the iron and iron salts washed with two 50 mL portions of water. Theyellow filtrate was acidified with 37% HCl to a pH of 1. At about a pHof 5, a white precipitate began to form. After cooling the acidifiedfiltrate at 5° C. overnight, the solid was collected by filtration,washed with water then acetone, and air dried. Approximately 14.3 g ofS-(4-aminophenylethyl)thiosulfuric acid was isolated.

To a slurry of 16 g S-(4-aminophenylethyl)thiosulfuric acid in 500 mL ofwater was added solid NaHCO₃ to adjust to pH to 8. As the pH was raisedthe solid dissolved yielding a solution of sodiumS-(4-aminophenylethyl)thiosulfate. To this was added a solution ofNa₂S•9H₂O (12.3 g) in 150 mL of water dropwise over the course of 30minutes with the concomitant formation of a precipitate. After theaddition was complete, the reaction mixture was stirred for 15 minutesand then extracted twice in a separatory funnel with first 200 mL then100 mL of ethyl acetate. The ethyl acetate extracts were combined anddried over MgSO₄. The ethyl acetate was evaporated leaving a yellowsolid. Final isolated yield of bis[2-(4-aminophenyl)ethyl]trisulfide was11.3 g.

To a stirred slurry of bis[2-(4-aminophenyl)ethyl]trisulfide (11.3 g),prepared as described above, in 300 mL of water was added a solution13.7 g of 37% HCl diluted in 100 mL of water. After stirring for 20minutes, an additional 200 mL of water was added and the mixture gentlyheated to 45° C. and stirred for 15 minutes to obtain a solution. Theresulting solution was cooled to room temperature and added to a stirredslurry of carbon black pellets (225 g) in 1.2 liters of water. Next, asolution of NaNO₂ (5.04 g) in 100 mL of water was added to the carbonblack slurry. Gas was evolved. The reaction mixture was stirredovernight and the carbon black product isolated by filtration, washedwith water, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.09% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.10 mmol/g ofattached -(4-C₆H₄)—CH₂CH₂—S—S—S—CH₂CH₂-(4-C₆H₄)— groups.

Example 125

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of bis(2-aminophenyl)disulfide in 500 mL of waterwas added a solution of 13.6 g of 37% HCl in 80 mL of water. Theresulting slurry was heated to 65° C. yielding a gold solution with abrown solid. After filtering the hot solution to remove the solid, thesolution was then added with stirring to a room temperature slurry ofcarbon black pellets (225 g) in 1.2 liters of water. A solution of NaNO₂(5.04 g) in 90 mL of water was then added to the carbon black slurryover the course of a minute. Gas was evolved. The mixture was stirredfor 2 hours, filtered and washed with water, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.44% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(2-C₆H₄)—S—S-(2-C₆H₄)— groups.

Example 126

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminophenyl)disulfide was prepared as follows frombis(3-nitrophenyl)disulfide following a procedure similar to the onedescribed by W. A. Sheppard in Organic Syntheses, Coll. Vol. 5, p. 843.To 13.7 g of solid 3-nitrobenzenesulfonyl chloride was added 46 mL of47% hydriodic acid (HI) yielding a dark brown mixture. The mixture wasrefluxed for 2.5 hours. During the course of the reaction, the iodineby-product sublimed into the water condenser and was removed atappropriate intervals to prevent clogging of the condenser. When thereaction mixture had cooled, NaHSO₃ was added to neutralize theremaining iodine. The resulting slurry was filtered to collect thesolid, and the solid was washed with 200 mL of water. The solid was thenextracted on the filter with 300 mL of acetone yielding an orangesolution. Removal of the acetone gave 8.4 g ofbis(3-nitrophenyl)disulfide as a orange solid.

To a stirred slurry bis(3-nitrophenyl)disulfide (8.4 g) in 100 mL ofwater was added a solution of Na₂S-9H₂O (20.4 g) in 100 mL of water. Thereaction mixture was heated to reflux at which point a dark red solutionwas obtained. After refluxing for 18 hours, an additional 5 g ofNa₂S•9H₂O was added to the reaction mixture and heating continued for 2hours. To the cooled reaction mixture was added 3.5 g of 30% H₂O₂ in adropwise manner. The white precipitate which formed was extracted twicewith 100 mL of ethyl acetate. The ethyl acetate extracts were combinedand dried over MgSO₄. Removal of the ethyl acetate gave 5.9 g ofbis(3-aminophenyl)disulfide.

To a stirred slurry of of bis(3-aminophenyl)disulfide (10.2 g), preparedas described above, in 0.7 liters of water was added a solution of 18 gof 37% HCl in 50 mL of water. This solution was cooled to 10° C., and asimilarly cooled solution of NaNO₂ (6.1 g) in 75 mL of water then added.This mixture was then added to a stirred slurry of carbon black pellets(225 g) in 1.8 liters of water. Gas was evolved. After stirring for 2hours, the carbon black product was isolated by filtration, washed withwater and dried at 115° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.71% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(3-C₆H₄)—S—S-(3-C₆H₄)— groups.

Example 127

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

6-amino-1,2,3-benzothiadiazole was prepared according to the methoddescribed in Ward, E. R.; Poesche, W. H.; Higgins, D.; and Heard, D. D.J. Chem. Soc. 1962, pp. 2374-2379. A solution of 3.5 g HCl in 50 mLwater was added to solid 6-amino-1,2,3-benzothiadiazole (2.38 g), andthe resulting solution cooled to 10° C. Next, a cold solution of NaNO₂(1.1 g) in 50 mL was added, and this mixture was then added to a stirredslurry of carbon black pellets (105 g) in 500 mL of water and 100 g ofice. Gas was evolved. After stirring the mixture for 3 hours, the carbonblack product was collected by filtration, washed with water andisopropanol, and air dried to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.50% sulfur, compared to 1.06% for theuntreated black. Therefore, the carbon black product had 0.14 mmol/g ofattached -6-(C₇H₅N₂S) groups.

Example 128

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(6-aminobenzothiazole)-2-sulfenamide was prepared asfollows. A solution of NaI₃ was prepared by adding 12 (35.5 g) to anaqueous solution consisting of NaI (47 g) dissolved in 150 mL of water.Next, 6-amino-2-mercaptobenzothiazole (6.5 g) was added to a solutionconsisting of NaOH (2.84 g) in 50 mL of water. After stirring for 15minutes, a red-brown solution was obtained to which morpholine (9.28 g)was added. To this mixture was added the previously prepared NaI₃solution. A brown precipitate formed and the slurry was stirred for 4hours. The solid was isolated by filtration and air dried. The solid wasslurried in 75 mL of ethanol and 3.34 g of morpholine. To this slurrywas added dropwise a solution of 3.24 g of 12 in 60 mL of ethanol overthe course of 20 minutes. After stirring the mixture at room temperatureovernight, the ethanol was removed on a rotary evaporator and theresidue washed with an aqueous solution of NaI to remove unreactediodine. The product was collected by filtration, washed with 250 mL ofwater, and then dried in a vacuum oven at 60° C. for 6 hours. 9.2 g ofN-morpholino-(6-aminobenzothiazole)-2-sulfenamide was isolated in 80%purity.

To a stirred slurry containing carbon black pellets (175 g),N-morpholino-(6-aminobenzothiazole)-2-sulfenamide (7.01 g) and NaNO₂(1.96 g) in 1 liter of water was added a solution consisting of 5.43 gof 37% HCl diluted in 75 mL of water. Gas was evolved. After stirringthe slurry for 48 hours, the carbon black product was filtered, washedwith water, and dried at 100° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.62% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.08 mmol/g ofattached -6-(2-C₇H₄NS)—S—NRR′ groups, where RR′ is —CH₂CH₂OCH₂CH₂—.

Example 129

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)tetrasulfide was prepared as follows. Under a nitrogenatmosphere, a solution of 9.74 g of 4-aminothiophenol in 150 mL ofanydrous tetrahydrofuran (THF) was prepared. The solution was thencooled in a dry ice/ethanol bath. Butyl lithium was added to the flaskand a thick yellow precipitate formed. Another 125 mL of THF was addedto the flask and the flask warmed in an ice water bath to 5° C. Sulfurmonochloride, S₂Cl₂, (2.80 mL) was added to the slurry over the courseof 5 seconds resulting in a red solution. After standing overnight at−15° C., the reaction mixture was warmed to room temperature and the THFremoved using a rotary evaporator. The orange oil was redissolved inCH₂Cl₂, filtered through Celite to remove insoluble LiCl and dried overMgSO₄. After filtering the solution to remove the MgSO₄, CH₂Cl₂ wasremoved yielding 11.4 g of bis(4-aminophenyl)tetrasulfide as an orangeoil.

A solution of 13 g of 37% HCl in 75 mL of water was added to a slurry ofbis(4-aminophenyl)tetrasulfide (10 g), prepared as described above, in200 mL of water, and the resulting mixture was stirred for 15 minutes.The orange-red suspension was cooled to 10° C., and a similarly cooledsolution of NaNO₂ (4.8 g) in 60 mL of water was added over the course of1-2 minutes. The resulting orange-yellow slurry was combined with astirred slurry of carbon black pellets (213 g) in 1 liter of water and200 g of ice. Gas was evolved. After stirring the mixture overnight, thecarbon black product was isolated by filtration, washed with water, anddried at 120° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.40% sulfur, compared to 1.23% for theuntreated black. Therefore, the carbon black product-had 0.09 mmol/g ofattached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 130

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)tetrasulfide was prepared as follows. To a stirredslurry of 4-nitrochlorobenzene (59 g) in 600 mL of water was added asolution consisting of Na₂S•9H₂O (240 g) dissolved in 200 mL of water.The resulting mixture was heated to reflux over the course of 45 minutesand continued for 17 hours. At the end of 17 hours a small amount of oilwas present in the flask. After allowing the reaction mixture to cool toroom temperature, the aqueous solution was decanted from the oil andthen filtered. Next, elemental sulfur powder (72 g) was added to theaqueous filtrate and the resulting slurry heated to reflux. After 22hours, a large amount of orange oil was present in the reaction. Heatwas removed and the reaction mixture cooled to room temperature. Theorange oil was extracted into 500 mL of ethyl acetate. Once the ethylacetate solution had been filtered and dried over MgSO₄, the ethylacetate was removed to give bis(4-aminophenyl)tetrasulfide as an orangeoil.

Bis(4-aminophenyl)tetrasulfide (10.5 g), prepared as described above,was stirred in 300 mL of water, and to this was added a solution of 13.7g of 37% HCl diluted in 100 mL of water. After stirring 15 minutes, anadditional 200 mL of water was added. Stirring for another 45 minutesyielded a finely divided suspension. The suspension was filtered toremove the solid, and the filtrate was combined with a stirred slurry ofcarbon black pellets (225 g) in 1.2 liters of water. Next, a solution ofNaNO₂ (5.04 g) in 50 mL of water was added to the carbon black slurry.Gas was evolved. After stirring the mixture overnight, the carbon blackproduct was isolated by filtration, washed with water and dried at 120°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.36% sulfur, compared to 1.09% for theuntreated black. Therefore, the carbon black product had 0.10 mmol/g ofattached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 131

A carbon black product having attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)—groups was prepared by following the method of Example 130 and using asuspension of 7.03 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 9.09 g of 37% HCl in 75 mL, a solution of 3.36 g of NaNO₂ in100 mL of water, and a slurry 225 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.63% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 132

A carbon black product having attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)—groups was prepared by following the method of Example 130 and using asuspension of 5.27 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 6.82 g of 37% HCl in 75 mL, a solution of 2.52 g of NaNO₂ in100 mL of water, and a slurry 225 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.54% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.03 mmol/g ofattached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 133

A carbon black product having attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)—groups was prepared by following the method of Example 130 and using asuspension of 3.22 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 4.16 g of 37% HCl in 75 mL, a solution of 1.54 g of NaNO₂ in100 mL of water, and a slurry 206 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.26% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.02 mmol/g ofattached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 134

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Liquid 4-aminostyrene (4.02 g) was added to a dilute aqueous acidsolution previously prepared by adding 7.33 g of 37% HCl to 150 mL ofwater. After stirring the mixture for 5 minutes, a yellow solution wasobtained and added to stirred slurry of carbon black pellets (225 g) in1.2 liters of water. Addition of a solution of NaNO₂ (2.94 g) dissolvedin 50 mL of water resulted in the formation of gas. After stirring themixture for 3 hours, the carbon black product was isolated byfiltration, washed with water, and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 0.46% hydrogen, compared to 0.37% for theuntreated black. Therefore, the carbon black product had 0.06 mmol/g ofattached -(4-C₆H₄)—CH═CH₂ groups.

Example 135

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

S-(4-aminophenyl)thiosulfuric acid (6.60 g) was prepared by the methoddescribed in Tanaka et al, Chem. Pharm. Bull. 1974, vol. 22, p. 2725,and was dissolved in 600 mL of water containing 3.50 g of 37% HCl. Thissolution was added to a stirred slurry of carbon black pellets (215 g)in 1.2 liters of water. Next, an aqueous solution of NaNO₂ (2.52 g) in30 mL of water was added to the slurry. Gas was evolved. After stirringthe mixture for 2 hours then standing overnight, the carbon blackproduct was isolated by filtration, washed with water, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.58% sulfur, compared to 1.23% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(4-C₆H₄)—S—SO₃H groups.

Example 136

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis[4-(4′-aminobenzenesulfonamido)phenyl]disulfide was prepared asfollows. To N-acetylsulfanilyl chloride (20.0 g) stirring in acetone(500 mL) at room temperature was added 4-aminophenyl disulfide (10.12 g)followed by pyridine (7.09 g). The cloudy yellow-orange reaction mixturewas allowed to stir for 20 hours, during which time a clear, goldenyellow solution formed. 7.5 mL of 37% HCl was added to 45 mL of water,and this acid solution was added to the reaction mixture. The acetonewas removed, and the remaining mixture was diluted with 100 mL of waterand extracted with ethyl acetate (2×200 mL). The combined ethyl acetateextracts were washed with water (5×100 mL), washed with a saturatedbrine solution (1×100 mL), dried over Na₂SO₄, and filtered. Removal ofthe ethyl acetate yielded 29.37 g of crude product as a tan foam. Thismaterial was added to a flask containing THF (150 mL), and 2N HCl (150mL) was added. The resulting slurry was heated to reflux. After 24 hoursat reflux, 48 mL of 2N HCl were added, and the reaction was continued atreflux for 22 hours. The clear orange solution was allowed to cool toroom temperature and carefully made basic with solid NaHCO₃, and theresulting mixture extracted with ethyl acetate (3×200 mL). The combinedethyl acetate extracts were washed with water (4×200 mL) until neutral,dried over Na₂SO₄, and filtered. Removal of the ethyl acetate yielded20.2 g of the desired product as a yellow solid.

Bis[4-(4′-aminobenzenesulfonamido)phenyl]disulfide (18.83 g), preparedas described above, was dissolved in a mixture of 500 mL of water, 632.4g of acetone, and 13.65 g of 37% HCl. This yellow solution was cooled inan ice water bath, and NaNO₂ (13.65 g) was added, yielding a deep redsolution containing an orange precipitate. This mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1/1 acetone/water (1.5 liters total). Gas was evolved. The slurry wasstirred overnight and filtered to collect the carbon black product. Thecarbon black product was washed with water, collected by filtration, anddried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.21% sulfur, compared to 1.14% for theuntreated black. Therefore, the carbon black product had 0.084 mmol/g ofattached -(4-C₆H₄)—SO₂NH-(4-C₆H₄)—S—S-(4-C₆H₄)—NHSO₂-(4-C₆H₄)— groups.

Example 137

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

p-Phenylenediamine (4.87 g) was dissolved in 250 mL of water containing9.11 g of 37% HCl. This was cooled in an ice bath, and a solution of3.36 g NaNO₂ dissolved in 125 mL of water was added. The resultingblue-green solution was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing280 g of ice. The slurry was stirred overnight and filtered to collectthe carbon black product. This product was washed with water, collectedby filtration, and dried at 125° C. to a constant weight.

Example 138

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

p-Phenylenediamine (2.43 g) was dissolved in 250 mL of water containing9.11 g of 37% HCl. This was cooled in an ice bath, and a solution of3.36 g NaNO₂ dissolved in 125 mL of water was added. This blue-greensolution was added in one portion to a rapidly stirring slurry of carbonblack pellets (225 g) in 2 liters of water containing 280 g of ice. Theslurry was stirred overnight and filtered to collect the carbon blackproduct. This product was washed with water, collected by filtration,and dried at 125° C. to a constant weight.

Example 139

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2,2′-bis(6-aminobenzothiazolyl)disulfide was prepared as follows.6-Amino-2-mercaptobenzothiazole (15.0 g) was added to 500 mL of water.To this slurry was added a solution of NaOH (3.3 g) dissolved in 1 literof water, and the mixture stirred for 1 hour at room temperature untilmost of the thiol was dissolved. A solution containing NaI (24.73 g) and12 (10.47 g) in 750 mL of water was added to the thiolate solutiongradually over 1.5 hours with vigorous stirring. During the addition, athick slurry containing a yellowish solid formed. After the addition andcontinued stirring for an additional 45 minutes, the solid was isolatedby filtration.

2,2′-bis(6-aminobenzothiazolyl)-disulfide (12.23 g), prepared asdescribed above, was added to 600 mL of water containing 13.66 g of 37%HCl. This yellow slurry was cooled in an ice bath, and a solution of5.04 g NaNO₂ dissolved in 50 mL of water was added. The resulting darkbrown mixture was added in one portion to a rapidly stirring slurry ofcarbon black pellets (225 g) in 2 liters of water containing 280 g ofice. The slurry was stirred overnight and filtered to collect the carbonblack product. The product was washed with water and isopropanol,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.69% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.054 mmol/g ofattached -6-(2-C₇H₄NS)—S—S-2-(6-C₇H₄NS)— groups.

Example 140

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-4-aminobenzyl sulfide was prepared as follows. A solutionof NaOH (7.1 g) in water (200 mL) was added to a mixture of4-aminothiophenol (19.8 g) in 190 mL of water. The mixture was stirreduntil most of the thiophenol was dissolved. To this mixture was added4-nitrobenzyl chloride (25.8 g) in portions with good stirring. Theresulting yellow solution was then stirred at reflux for 1.5 hours,during which time a thick red oil separated. At the end of the reaction,the mixture was allowed to cool to room temperature, and the red oilseparated as a waxy solid. The solid was extracted with ethyl acetate(400 mL followed by 100 mL), and the combined ethyl acetate extractswere dried over Na₂SO₄ and filtered. Removal of the ethyl acetateyielded 38.65 g of 4-aminophenyl-4-nitrobenzyl sulfide.

All of the above product was dissolved in a mixture of ethanol (235 mL)and water (780 mL). To this solution was added 37% HCl (27.83 g) andiron powder (49.78 g), and the slurry stirred at reflux for 3 hours.After cooling to room temperature, 200 mL of water were added, and themixture was extracted with ethyl acetate (600 mL followed by 200 mL).The combined ethyl acetate extracts were dried over Na₂SO₄ and filtered.Removal of the ethyl acetate yielded 31.53 g of the desired product.

4-aminophenyl-4-aminobenzyl sulfide (7.77 g), prepared as describedabove, was added to 250 mL of water containing 13.7 g of 37% HCl. Theresulting solution was cooled in an ice bath and a solution of 5.04 gNaNO₂ dissolved in 125 mL of water added. The resulting mixture wasadded in one portion to a rapidly stirring slurry of carbon blackpellets (225 g) in 2 liters of water containing 280 g of ice. The slurrywas stirred overnight and filtered to collect the carbon black product.This product was collected by filtration, washed with water then withethanol, collected by filtration, and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.38% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.12 mmol/g ofattached -(4-C₆—H₄)—S—CH₂-(4-C₆H₄)— groups.

Example 141

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)thiosulfonate was prepared following a modifiedprocedure to the one described in Leitch, L.; Baker, B.; Brickman, L.Can. J. Res. Sect. B 1945, 23, 139. To a well-stirred mixture ofthiourea (11.4 g) in acetone (175 mL) was added pyridine (16.85 mL)followed by N-acetylsulfanilyl chloride (35.05 g). A yellow colordeveloped. This mixture was heated to reflux and stirred under theseconditions for 80 minutes. The reaction was then allowed to cool to roomtemperature, and a fluffy solid precipitated. After removing theacetone, 500 mL of hot water were added. A pale yellow precipitateformed, which was isolated by filtration, yielding 22.7 g ofbis(4-acetamidophenyl)thiosulfonate.

The desired final product was obtained following a modification to theprocedure described in Bere, C.; Smiles, S. J. Chem. Soc. 1924, 2359.All of the bis-(4-acetamidophenyl)thiosulfanate prepared above (22.7 g)was dissolved in 250 mL of THF, and 250 mL of 2N HCl was added. Themixture was heated to reflux and stirred for 5 hours. After allowing thereaction to cool to room temperature, most of the THF was removed andsolid NaHCO₃ added carefully until no further gas evolution was seen. Anorange precipitate formed, which was isolated by filtration, yieldingthe desired bis(4-aminophenyl)thiosulfonate (10.3 g).

Bis(4-aminophenyl)thiosulfonate (9.46 g), prepared as described above,was added to 250 mL of water containing 13.65 g of 37% HCl, and thecloudy yellow mixture cooled in an ice bath. To this was added asolution of 5.04 g NaNO₂ dissolved in 125 mL of water. A yellowcolloidal suspension formed. The resulting mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. The productwas washed with water and collected by filtration. This was then washedwith ethanol, collected by filtration, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.85% sulfur, compared to 1.30% for theuntreated black. Therefore, the carbon black product had 0.086 mmol/g ofattached -(4-C₆H₄)—SO₂—S-(4-C₆H₄)— groups.

Example 142

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminobenzyl)sulfide was prepared as follows. A solution of4-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added slowly, withgood stirring, to a solution of Na₂S•9H₂O (43.2 g) in 1 liter of water.The mixture was stirred at room temperature for 18 hours. Removal of theTHF and filtration yielded 46.8 g of bis(4-nitrobenzyl)sulfide.

All of this material was dissolved in 530 mL of ethanol. Water (1.1liters) was added followed by 530 mL of 2N HCl and 69.1 g of ironpowder. While stirring vigorously, the mixture was heated at reflux for3 hours. After cooling to room temperature, 800 mL of water were added,and the reaction mixture was extracted with 1900 mL of ethyl acetate inseveral portions. The combined ethyl acetate extracts were dried overNa₂SO₄, and filtered. Removal of the ethyl acetate yielded 28.9 g of thedesired bis(4-aminobenzyl)sulfide.

Bis(4-aminobenzyl)sulfide (12.8 g), prepared as described above, wasadded to 700 mL of water containing 21.3 g of 37% HCl. The resultingsolution was stirred for 2 hours and then cooled in an ice bath. Asolution of 7.84 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (350 g) in 2.5 liters ofwater containing 280 g of ice. The slurry was stirred overnight and thenfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.34% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆H₄)—CH₂—S—CH₂-(4-C₆H₄)— groups.

Example 143

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminobenzyl)sulfide (10.99 g), prepared as described for Example142 above, was added to 700 mL of water containing 18.2 g of 37% HCl.After stirring for 2 hours, the solution was cooled in an ice bath. Asolution of 6.72 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (225 g) in 2 liters ofwater containing 280 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.40% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.125 mmol/g ofattached -(4-C₆H₄)—CH₂—S—CH₂-(4-C₆H₄)— groups.

Example 144

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl)sulfide was prepared as follows. A solution of3-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added to a solutionof Na₂S•9H₂O (43.2 g) in 1 liter of water slowly with good stirring.This mixture was stirred at room temperature for 18 hours. Removal ofthe THF and filtration yielded 45.8 g of bis(3-nitrobenzyl)sulfide.

All of this material was dissolved in 530 mL of ethanol. 1.1 liters ofwater was added followed by 140 mL of 2N HCl and 67.64 g of iron powder.While stirring vigorously, the mixture was heated to reflux for 4.5hours. More iron powder (15.0 g) was added, and the reaction wascontinued at reflux for an additional 1 hour. After cooling to roomtemperature, the reaction mixture was extracted several times with ethylacetate. The combined ethyl acetate extracts were dried over Na₂SO₄, andfiltered. Removal of the ethyl acetate yielded 33.1 g of the desiredbis(3-aminobenzyl)sulfide.

Bis(3-aminobenzyl)sulfide (10.99 g), prepared as described above, wasadded to 400 mL of water containing 18.2 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 6.72g NaNO₂ dissolved in 75 mL of water was added. The resulting browncolloidal suspension was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing280 g of ice. The slurry was stirred overnight and filtered to collectthe carbon black product. The product was washed with ethanol then withwater, collected by filtration, and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.50% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(3-C₆H₄)—CH₂—S—CH₂-(3-C₆H₄)— groups.

Example 145

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl)sulfide (16.48 g), prepared as described for Example144 above, was added to 500 mL of water containing 27.32 g of 37% HCl.After stirring for 2 hours, the solution was cooled in an ice bath. Asolution of 10.1 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (450 g) in 3 liters ofwater containing 300 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.30% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.094 mmol/g ofattached -(3-C₆H₄)—CH₂—S—CH₂-(3-C₆H₄)— groups.

Example 146

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminobenzyl)disulfide was prepared as follows. A mixture of4-nitrobenzyl chloride (40.0 g) in 933 mL of methanol and 233 mL orwater was heated until a solution formed. To this was added slowly, withgood stirring, a solution of Na₂S₂O₃•5H₂O (72.34 g) in 233 mL of water.This mixture was then stirred at reflux for 4 hours. After cooling toroom temperature, most of the methanol was removed, and to the aqueoussolution (approximately 300 mL) was added a solution of Na₂CO₃ in 600 mLof water. This was stirred at room temperature for 18 hours, duringwhich time a cream colored opaque mixture formed. The precipitate wasisolated by filtration and washed with water yielding 37.1 g ofbis(4-nitrobenzyl)disulfide.

Bis(4-nitrobenzyl)disulfide (10.0 g) was dissolved in 1.5 liters ofethanol (heating to approximately 73° followed by filtration was neededin order to obtain a clear solution). To this heated solution was added0.5 liters of water, 30 mL of 2N HCl, and 16.4 g of iron powder. Thetemperature was then allowed to drop to approximately 45°, and thereaction was continued at this temperature for 8 hours. The reactionmixture was then heated to reflux and allowed to continue for 3.5 hours.After cooling to room temperature, the mixture was then extractedseveral times with ethyl acetate. The combined ethyl acetate extractswere dried over Na₂SO₄, and filtered. Removal of the ethyl acetateyielded 4.69 g of the desired bis(4-aminobenzyl)disulfide.

Bis(4-aminobenzyl)disulfide (9.32 g), prepared as described above, wasadded to 250 mL of water containing 13.66 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 5.04g NaNO₂ dissolved in 125 mL of water was added. This mixture was addedin one portion to a rapidly stirring slurry of carbon black pellets (225g) in 2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. The productwas washed with ethanol then with water, collected by filtration, anddried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.55% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.086 mmol/g ofattached -(4-C₆H₄)—CH₂—S—S—CH₂-(4-C₆H₄)— groups.

Example 147

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl)disulfide was prepared as follows. A solution ofNa₂S₂O₃•5H₂O (72.34 g) in 233 mL of water was added slowly, with goodstirring, to a solution of 3-nitrobenzyl chloride (40.0 g) in 933 mL ofmethanol and 233 mL of water. The resulting mixture was then stirred atreflux for 4 hours. After cooling to room temperature, most of themethanol was removed, and the aqueous layer was extracted with ethylacetate. Removal of the water from the aqueous layer yielded 69.04 g ofthe sodium salt of 3-nitrobenzyl thiosulfate.

A solution of Na₂CO₃ (124.83 g) in 1 liter of water was gradually addedto a solution of the sodium salt of 3-nitrobenzyl thiosulfate (39.21 g)in 800 mL of water with good stirring. After stirring at roomtemperature for 18 hours, a cream colored opaque mixture formed. Theprecipitate was isolated by filtration and washed with water yielding16.8 g of bis(3-nitrobenzyl)disulfide.

Bis(3-nitrobenzyl)disulfide (7.5 g) was dissolved in 1.5 liters ofethanol (this was heated and then filtered while warm in order to obtaina clear solution). To this heated solution was added 750 mL of water,22.5 mL of 2N HCl, and 12.3 g of iron powder. The reaction was thenfurther heated to just below the reflux temperature, and heating wascontinued for 5 hours. After cooling to room temperature, 400 mL ofwater was added, and the mixture was then extracted several times withethyl acetate. The combined ethyl acetate extracts were dried overNa₂SO₄, and filtered. Removal of the ethyl acetate yielded 5.15 g of thedesired bis(3-aminobenzyl)disulfide.

Bis(3-aminobenzyl)disulfide (9.99 g), prepared as described above, wasadded to 250 mL of water containing 14.6 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 5.4 gNaNO₂ dissolved in 125 mL of water was added. This mixture was added inone portion to a rapidly stirring slurry of carbon black pellets (241 g)in 2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. This productwashed with ethanol then with water, collected by filtration, and driedat 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.62% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.097 mmol/g ofattached -(3-C₆H₄)—CH₂—S—S—CH₂-(3-C₆H₄)— groups.

Example 148

This example further illustrates the in situ method of preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(4-aminophenyl)sulfenamide was prepared as follows. Asolution of 12 (14.2 g) in ethanol (300 mL) was added to a well-stirredsolution containing 4-diaminophenyl disulfide (13.9 g) and morpholine(24.4 g) in ethanol (300 mL). The reaction mixture was stirred at roomtemperature for 3 hours. Removal of the ethanol gave a thick, nearlyblack oil. It was redissolved in 750 mL of ethyl acetate and washedseveral times with water. The ethyl acetate layer was dried over Na₂SO₄,and filtered. Removal of the ethyl acetate yielded 19.6 g of the desiredN-morpholino-(4-aminophenyl)sulfenamide.

N-morpholino-(4-aminophenyl)sulfenamide (9.46 g), prepared as describedabove, was added to a well-stirred mixture of carbon black (225 g), ice(280 g), and water (2 liters). To this was added a solution of 3.36 gNaNO2 dissolved in 75 mL of water followed by addition of a solution of37% HCl (4.66 g) in 75 mL of water. The slurry was stirred for 5 hours,filtered to collect the carbon black product, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.26% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.02 mmol/g ofattached -(4-C₆H₄)—S—NRR′ groups where RR′ is —CH₂CH₂OCH₂CH₂—.

Example 149

This example further illustrates the in situ method of preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(4-aminophenyl)sulfenamide (9.46 g), prepared as describedfor Example 148 above, was added to a well-stirred mixture of carbonblack (225 g), ice (280 g), and water (2 liters). To this was added asolution of 3.36 g NaNO₂ dissolved in 75 mL of water followed byaddition of a solution of 37% HCl (9.32 g) in 75 mL of water. The slurrywas stirred for 5 hours, filtered to collect the carbon black product,and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.34% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.04 mmol/g ofattached -(4-C₆H₄)—S—NRR′ groups where RR′ is —CH₂CH₂OCH₂CH₂—.

Example 150

This example further illustrates the method of preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis[2-(4-aminobenzenesulfonamido)ethyl]disulfide was prepared asfollows. To a well-stirred mixture of N-acetylsulfanilyl chloride (1.26g) in 50 mL of CH₂Cl₂ in an ice bath was added triethylamine (559 mg)followed by cystamine (2,2′-diaminoethyl disulfide, 400 mg). The icebath was removed, and the reaction was stirred for 18 hours at roomtemperature. Removal of the CH₂Cl₂ gave a brownish-yellow solid, whichwas stirred vigorously in 50 mL of water for 3 hours and filtered togive 1.24 g of bis[2-(4-acetamidobenzenesulfonamido)ethyl]disulfide.

A sample of bis[2-(4-acetamidobenzenesulfonamido)ethyl]disulfide (1.00g) was heated to reflux in a mixture of 40 mL of ethanol and 40 mL of 2N HCl, and stirred at this temperature for 3 hours. After cooling toroom temperature, 200 mL of water were added and the mixture made basicby carefully adding solid NaHCO₃. A white precipitate formed which wasisolated by extraction of the basic aqueous layer with ethyl acetate(2×150 mL). The combined ethyl acetate extracts were dried over Na₂SO₄and filtered. Removal of the ethyl acetate yielded 735 mg of the desiredbis[2-(4-aminobenzenesulfonamido)ethyl]disulfide.

Bis[2-(4-aminobenzenesulfonamido)ethyl]disulfide (15.6 g), prepared asdescribed above, was added to 275 mL of water containing 13.6 g of 37%HCl and the mixture cooled in an ice bath. Next, a solution of 5.04 gNaNO₂ dissolved in 60 mL of water was added to the mixture. Theresulting yellow slurry was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 1.2 liters of water. Theslurry was stirred overnight and filtered to collect the carbon blackproduct. This product was washed with water, collected by filtration,and dried at 100° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.06% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆H₄)—SO₂NH—CH₂CH₂—S—S—CH₂CH₂—NHSO₂-(4-C₆H₄)— groups.

Example 151

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2-(4-aminophenyl)-1,3-dithiane was prepared following a modification tothe procedure described in Truce, W.; Roberts, F J. Org. Chem. 1963, 28,961. To a well-stirred mixture of 4-acetamidobenzaldehyde (12.7 g) in200 mL of acetic acid was added MgCl₂ (5.57 g) followed by 1,3-propanedithiol (8.44 g). The reaction mixture turned white upon addition of thedithiol. This mixture was stirred at room temperature for 2 hours. Thewhite precipitate was isolated by filtration, washed several times withwater, and dried to give 12.5 g of 2-(4-acetamidophenyl)-1,3-dithiane.

All 12.5 g of 2-(4-acetamidophenyl)-1,3-dithiane was dissolved in 150 mLof ethanol. A total of 150 mL of 2N HCl was added, and the reactionmixture was heated to reflux. After reacting at this temperature for 6hours, the clear yellow solution was allowed to cool to room temperatureand then made basic with a dilute NaOH solution. The resulting lightyellow precipitate was isolated by filtration, washed with water untilneutral, and dried to yield 14.8 g of the desired2-(4-aminophenyl)-1,3-dithiane.

2-(4-aminophenyl)-1,3-dithiane (7.13 g), prepared as described above,was added to 250 mL of water containing 6.83 g of 37% HCl and was cooledin an ice bath. A solution of 2.52 g NaNO₂ dissolved in 125 mL of waterwas added. This mixture was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing200 g of ice. The slurry was stirred for 4.5 hours and filtered tocollect the carbon black product. This product was washed with water,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.65% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆H₄)-2-(1,3-dithiane) groups.

Example 152

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2-(4-aminophenyl)-1,3-dithiane (4.75 g), prepared as described inExample 151 above, was added to 250 mL of water containing 4.55 g of 37%HCl. Next, the mixture was cooled in an ice bath and a solution of 1.68g NaNO₂ dissolved in 125 mL of water was added. The resulting mixturewas added in one portion to a rapidly stirring slurry of carbon blackpellets (112.5 g) in 2 liters of water containing 100 g of ice. Theslurry was stirred for 4.5 hours and filtered to collect the carbonblack product. This product was washed with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.47% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.04 mmol/g ofattached -(4-C₆H₄)-2-(1,3-dithiane) groups.

Example 153

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

N,N′-bis-(4-aminophenyl)-piperazinosulfenamide was prepared as follows.A solution of 12 (21.6 g) in 800 mL of ethanol was added to awell-stirred solution of 4,4-diaminophenyldisulfide (21.3 g) andpiperazine (36.7 g) in 1 liter of ethanol at room temperature. The darkcolored reaction mixture was stirred at this temperature for 16 hoursand then filtered. The cream colored precipitate was washed with waterand filtered to yield 25.1 g of the desiredN,N′-bis-(4-aminophenyl)-piperazinosulfenamide.

N,N′-bis-(4-aminophenyl)-piperazinosulfenamide (11.2 g), prepared asdescribed above, was added to a well-stirred mixture of carbon black(225 g), ice (280 g), and water (2 liters). To this was added a solutionof 5.04 g NaNO₂ dissolved in 75 mL of water followed by a solution of37% HCl (13.65 g) in 75 mL of water. The slurry was stirred overnightand filtered to collect the carbon black product. The product was washedwith water, filtered, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.91% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆H₄)—S-(1,4-C₄H₈N₂)—S-(4-C₆H₄)— groups.

Example 154

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)disulfide (4.19 g) was dissolved in 230 mL of watercontaining 7.32 g of 37% HCl. The solution was then cooled in an icebath and a solution of 2.64 g NaNO₂ dissolved in 40 mL of water added.This mixture was added in one portion to a rapidly stirring slurry ofcarbon black pellets (225 g) in 1200 mL of water containing a smallamount of ice. The slurry was stirred for 2 hours and filtered tocollect the carbon black product. This product was washed with ethanol,then with water, collected by filtration, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.55% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 155

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)disulfide (8.55 g) was dissolved in 180 mL of watercontaining 14.65 g of 37% HCl. The solution was then cooled in an icebath and 50 mL of ethanol was added followed by addition of a solutionof 5.28 g NaNO2 dissolved in 35 mL of water. This mixture was added inseveral portions to a rapidly stirring slurry of carbon black pellets(225 g) in 1200 mL of water containing a small amount of ice. The slurrywas stirred for 2 hours and filtered to collect the carbon blackproduct. This product was washed with ethanol, then with water,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.82% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 156

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/00 g was used.

Bis(4-aminophenyl)disulfide (1.18 g) was dissolved in 560 mL of watercontaining 19.53 g of 37% HCl. The solution was cooled in an ice bathand a solution of 7.04 g NaNO2 dissolved in 60 mL of water added. Anadditional 150 mL of water was added, and the mixture added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.26% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.18 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 157

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)disulfide (13.97 g) was dissolved in 560 mL of watercontaining 24.4 g of 37% HCl. The solution was cooled in an ice bath anda solution of 8.80 g NaNO₂ dissolved in 60 mL of water added. Anadditional 150 mL of water was added and the resulting mixture added inone portion to a rapidly stirring slurry of carbon black pellets (225 g)in 1200 mL of water containing a small amount of ice. The slurry wasstirred for 3.5 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.50% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.22 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 158

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)disulfide (17.1 g) was dissolved in 175 mL of watercontaining 29.30 g of 37% HCl. The resulting solution was cooled in anice bath and a solution of 10.6 g NaNO2 dissolved in 60 mL of wateradded. 100 mL of ethanol was added, and this mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.55% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.23 mmol/g ofattached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 159 Comparative Carbon Black Products

In this comparative example, the carbon black used in Example 118-158was washed with water, ethanol and water and subsequently dried to givethe comparative carbon black product.

Example 160 Comparative Carbon Black Products

In this comparative example, the carbon black used in Examples 118-158was used without modification and serves as the comparative carbon blackproduct.

Use of Carbon Black Products in Rubber Formulations

The carbon black products described in Examples 118-158 can be used in avariety of elastomers. The elastomers include, but are not limited to,the following types: solution SBR, functionalized (tin coupled and/orchemically modified and/or other functional-ization) solution SBR,natural rubber, emulsion SBR, polybutadiene, and terpolymers. Theseelastomers may appear in rubber formulations alone or as blends.

NS 116 and NS 114 are chemically modified tin coupled solution SBRsavailable from Nippon Zeon, Japan. Duradene 715 is a solution SBR.Duradene is a registered trademark for SBR products available fromFirestone, Akron Ohio. S 1216 is a solution SBR available from GoodyearTire and Rubber Co., Akron Ohio. SBR-1500 is an emulsion SBR availablefrom Copolymer Rubber and Chemical Corp., Baton Rouge, La. SL-574 is atin coupled solution SBR available from Japan Synthetic Rubber Co.(JSR), Japan. RCT0586 and T0587 are chemically modified solution SBRsalso available from JSR. Flexzone is a registered trademark forantidegradent products available from Uniroyal Chemical, Naugatuck,Conn. CBS is N-cyclohexylbenzothiazylsulfenamide, MBT is2-mercaptobenzothiazole and DTDM is N,N′-dithiodimorpholine.

Examples 161-166

These examples illustrate the use of the carbon black products ofExamples 118, 121, 122 and the comparative Example 160 in two differentrubber formulations. The polymer was milled in a Brabender mixer for 1minute at 100° C. The carbon black product or comparative carbon blackwas added and mixed for 3 additional minutes or until a temperature of160° C. was reached. The mixture was then dumped and passed through anopen mill 3 times. After allowing the compound to stand at roomtemperature for 2 hours, it was transferred back into the Brabender andmixed for 1 minute at 100° C. After 1 minute, ZnO and stearic acid wereadded and mixed for 2 minutes and then Flexzone 7P antidegradent wasadded and mixed for an additional minute or until a temperature of 160°C. was reached. The sample was then dumped, passed through an open mill3 times and allowed to stand at room temperature for 2 hours. The samplewas placed back into the Brabender and mixed for 1 minute at 100° C. Thecuratives were then added and mixed for 1 minute and the sample thendumped and passed through an open mill 3 times. The formulations usedwere selected from Table I.

The data in Table II show that carbon black products of the presentinvention are useful in rubber formulations. In the case where a blendof NS-116 and NS-114 was used, significant increases in 100% modulus,bound rubber, tensile strength, hardness and abrasion resistance can beobtained, as can significant decreases in Tan δ. In Duradene 715, highermodulus, hardness, and bound rubber are obtained, while tensilestrength, elongation at break and 70° C. Tan δ are reduced. Themagnitude of the effect depends on the specific groups attached to thecarbon black product.

Examples 167-180

These examples illustrate the use of the carbon black products ofExamples 121-124 and the comparative Example 160 in several differentrubber formulations. With the exception of those formulations containingDTDM, rubber compounds were prepared by the method described forExamples 161-166 using formulations selected from Table I. A slightchange in the mixing procedure was made for those rubber compoundscontaining DTDM. In this case, the samples with DTDM were mixed for 3minutes after addition of the Flexzone 7P, after which, the mixingprocedure described for Examples 161-166 was followed.

The performance data in Table III show that carbon black productsaccording to the invention are useful in several different rubberformulations. In particular, carbon black products described in Examples4 and 5 reduce 70° C. Tan δ when using natural rubber, SBR-1500, orDuradene 715 in the formulation. Furthermore, addition of 0.8 phr ofDTDM to the rubber formulations containing carbon black products ofExamples 4 and 5 gives vulcanizates with higher hardness, modulus, andbound rubber, relative to the formulation without DTDM. It also resultsin lower elongation and 70° C. Tan δ and, in general, gives greatertensile strength and improved abrasion resistance.

Examples 181-188

These examples illustrate the use of the carbon black products ofExamples 120, 126, 139 and 140 and the comparative Example 160 inseveral different rubber formulations. The rubber compounds wereprepared by the method described for Examples 161-166 using formulationsselected Table I.

The performance data in Table IV show that carbon black productsaccording to the invention are useful in several different rubberformulations. Specifically, in a blend of NS-116 and NS-114, use ofcarbon black products from Examples 120, 126, 139 and 140 gave increasedbound rubber and significant reductions in 70° C. Tan δ. In Duradene,carbon black products described in Examples 9 and 23 are especiallyuseful in reducing 70° C. Tan δ.

Examples 189-196

These examples illustrate the use of the carbon black products ofExamples 123, 127, 134 and 136 and the comparative Example 159 inseveral different rubber formulations. The rubber compounds wereprepared by the following method using formulations selected from TableI.

The polymer was milled in a Brabender mixer for 1 minute at 100° C. Amixture of ZnO and the carbon black product or comparative carbon blackwas added and mixed for 2 additional minutes. The stearic acid andFlexzone 7P antidegradent were added and mixed for 2 additional minutes.The sample was dumped and passed through an open mill 3 times. Thesample was allowed to cool and then transferred back into the Brabendermixer and mixed for 1 minute at 100° C. The curative package was thenadded, mixing continued for 1 minute, and the sample dumped then passedthrough a open mill 3 times.

Table V shows that these carbon black products are useful in severalrubber formulations including functionalized and unfunctionalizedsolution SBRs. Furthermore, use of carbon black product described inExample 123 in S-1216, Duradene 715, and NS-116 results in lower 70° C.Tan δ values as well as increased bound rubber. When compounded withNS-114, the carbon black product from Example 127 gave higher modulus,bound rubber and abrasion resistance, lower elongation and 70° C. Tan δ,and equal tensile strength and hardness.

Examples 197-200

These examples illustrate the use of the carbon black products ofExamples 129 and 135 and the comparative Example 160 in two differentrubber formulations. The rubber compounds were prepared by the themethod described in Examples 189-196 using formulations selected fromTable I.

Table VI shows that these carbon black products are useful in theserubber formulations using functionalized or unfunctionalized solutionSBRs. When using a blend of NS-116 and NS-114, increases in modulus,hardness, and bound rubber were observed. Sizable decreases in 70° C.Tan δ and elongation are also seen. In Duradene 715, modulus wasincreased while tensile strength, elongation at break, and 70° C. Tan δare all substantially reduced.

Examples 201-205

These examples illustrate the use of the carbon black products ofExample 155 and the comparative Example 160 in different rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

Table VII shows that this carbon black product was useful in a number ofrubber formulations, specifically formulations that contained NR,emulsion SBR, or a functionalized solution SBRs selected from SL-574,RCTO-586, or TO-587.

Examples 206-215

These examples illustrate the use of the carbon black products ofExamples 154-158 and the comparative Example 159 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

As can be seen by inspection of the data in Table VIII below, a widerange of treatment levels as exemplified by the carbon black products inExamples 154-158 can have an impact on rubber performance properties.

Examples 216-221

These examples illustrate the use of the carbon black products ofExamples 137, 138, and 141 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table IX shows that these carbon black products were useful in severalrubber formulations including functionalized and unfunctionalizedsolution SBRs. In particular, the carbon black products in Examples 137,138, and 141 all showed lower 70° C. Tan δ values as well as increasedbound rubber in both rubber systems. In addition, the products inExample 137 and 138 also showed improvements in abrasion resistance.

Examples 222-235

These examples illustrate the use of the carbon black products ofExamples 142-147 and the comparative Example 160 in three rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table X shows that these carbon black products were useful in the rubberformulations studied. In particular, all of the blacks studied showedreductions in 70° C. Tan δ values and increased bound rubber in bothfunctionalized and unfunctionalized solution SBRs with comparablehardness. Comparable hardness and 70° C. Tan δ values were found innatural rubber, with the carbon black product of Example 146 showing thegreatest reduction in Tan δ.

Examples 236-246

These examples illustrate the use of the carbon black products ofExamples 148-153 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table XI shows that these carbon black products were useful in rubberformu-lations. For example, when the carbon black products of Example148, 149, and 153 were compounded in Duradene 715 or a 70/30 blend ofNS-116 and NS-114, in general, abrasion resistance is either unchangedor improved while 70° C. Tan δ values were reduced.

Examples 247-262

These examples illustrate the use of the carbon black products ofExamples 119, 125, 128 and 130-133 and the comparative Example 160 invarious rubber formulations. The rubber compounds were prepared by thethe method described in Examples 161-166 using formulations selectedfrom Table I.

Table XII shows that these carbon black products were useful in rubberformu-lations. For example, when the carbon black product of Example 119was compounded with Duradene 715, SBR-1500, or a blend of NS-116 andNS-114, abrasion resistance was improved while 70° C. Tan δ values werereduced and the percentage of bound rubber increased. Use of carbonblack products from Examples 130-133 in Duradene 715 and Natural Rubbershowed that a wide range of carbon black treatment levels of this typecan have an impact on rubber performance properties.

Example 263 Preparation of a Carbon Black Product

Ten grams of a carbon black with a surface area of 230 m2/g and a DBPAof 70 m2/g was added to a stirring solution of 3.06 g of3-amino-N-ethylpyridinium bromide in 72 g of water. Concentrated nitricacid (1.62 g) was added, and the mixture was stirred and heated to about70° C. A solution of 1.07 g NaNO₂ in about 5 g of water was added over afew minutes. The diazonium salt N₂C₅H₄N(C₂H₅)⁺⁺ was formed in situ,which reacted with the carbon black. After the reaction mixture wasstirred for one hour, the sample was dried in an oven at 125°. Theproduct had a mean volume particle size of 0.18 microns. The product hadattached 3-C₅H₄N(C₂H₅)⁺ groups.

Example 264 Preparation of a Carbon Black Product

3-Amino-N-methylpyridinium iodide (3.92 g) was dissolved in 70 g ofwater. A solution of 2.58 g AgNO₃ in 6 g of water was added. Afterstirring for 15 minutes, the precipitate was removed by filtration and10 g of a carbon black with a surface area of 230 m2/g and a DBPA of 70m2/g was added. Concentrated nitric acid (1.62 g) was added, and themixture was stirred and heated to about 70°. A solution of 1.07 g NaNO₂in about 5 g of water was added over a few minutes. The diazonium saltN₂C₅H₄CH₂N(CH₃)⁺⁺ was formed in situ, which reacted with the carbonblack. Bubbles were released. After the reaction mixture was stirred forabout 40 minutes at 70° and then boiled for about 15 minutes. The samplewas dried in an oven at 125°. The product had a mean volume particlesize of 0.23 microns. The product had a 325 mesh residue of 0.0%compared to 94% for the untreated carbon black. The product had attached3-C₅H₄N(CH₃)⁺ groups.

Example 265 Preparation of a Carbon Black Product

Fifty grams of benzyltrimethylammonium chloride was added over 25minutes to cold 90% nitric acid. The mixture was kept below 10° C. forfive hours. Ice (500 g) was added, and the mixture was neutralized withKOH. The precipitate was removed by filtration. Ethanol (1 L) was addedand the mixture was filtered again. 3-Nitrobenzyltrimethylammoniumnitrate was recovered from the filtrate. This material was 75% pure byNMR. A mixture of 10 g of 3-Nitrobenzyltrimethylammonium nitrate, 14 gFe filings, 2 g of concentrated HCl and 400 g of water was boiled for2.5 hr. The mixture was neutralized with KOH and filtered to give anaqueous solution of 3-aminobenzyltrimethylammonium nitrate/chloride.

Fourteen grams of carbon black with a surface area of 230 m2/g and aDBPA of 70 m2/g was added to a stirring solution of 3.06 g of3-aminobenzyltrimethylammonium nitrate/chloride in 72 g of water.Concentrated nitric acid (1.62 g) was added, and the mixture was stirredand heated to about 70° C. A solution of 1.07 g NaNO₂ in about 5 g ofwater was added over a few minutes. The diazonium salt 3-N₂C₆H₄N(CH₃)⁺⁺was formed in situ, which reacted with the carbon black. After thereaction mixture was stirred for one hour, the sample was dried in anoven at 125° C. The product had a mean volume particle size of 0.18microns. The product had attached 3-N₂C₆H₄CH₂N(CH₃)₃ ⁺ groups.

Example 266 Preparation of a Carbon Black Product

Silver nitrite (30.9 g) was added to a solution of 41.4 g ofN-(4-aminophenyl)pyridinium chloride in 700 g of water and the mixturewas stirred at 70° for 1½ hours. The mixture was filtered and 200 g of acarbon black with a surface area of 200 m2/g and a DBPA of 122 mL/100 gwas added. An additional one liter of water and 20 g of concentrated HClwere added. The diazonium salt N₂C₆H₄NC₅H₅ ⁺⁺ was formed in situ, whichreacted with the carbon black. Bubbles were released. The dispersion wasstirred at 70-80° for 2½ hours and then dried in an oven at 125° C. Theproduct had attached C₆H₄NC₅H₅ ⁺ groups.

Example 267 Preparation of a Carbon Black Product

In a modification of a procedure from U.S. Pat. No. 2,821,526, a mixtureof 250 g p-acetaminophenacyl chloride, 65 g of trimethylamine and about600 g of water was stirred for three days at room temperature. Anadditional 5 g of trimethylamine in 15 g water was added and the mixturewas heated at 60° for two hours. After cooling and filtering, 201 gconcentrated HCl was added and the solution was boiled for an hour.After cooling, 4 L of acetone was added and4-aminophenacyltrimethylammonium chloride hydrochloride was collected asa solid. 4-Aminophenacyltrimethylammonium chloride hydrochloride (10.1g) was suspended in 50 mL of ethanol. After addition of 4.1 gtriethylamine, the mixture was stirred for 40 minutes and heated atreflux for one hour. 4-Aminophenacyl-trimethylammonium chloride wascollected by filtration and washed with ethanol.

4-Aminophenacyltrimethylammonium chloride (2.51 g) was dissolved inwater. Silver nitrite (1.69 g) was added, and the mixture was heated at70° for one hour. After filtering off the precipitate, 10 g of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 mL/100 g wasadded. Water was added to bring the volume up to about 100 mL.Concentrated HCl (1.1 g) was added and the dispersion was heated withstirring at 70° for one hour. The diazonium salt N₂C₆H₄COCH₂N(CH₃)₃ ⁺⁺was formed in situ, which reacted with the carbon black. Bubbles werereleased. The product had attached C₆H₄COCH₂N(CH₃)₃ ⁺ groups.

Example 268 Preparation of a Carbon Black Product

A solution of 2.12 g of 4-acetaminophenacyl chloride, 0.83 g of pyridineand 6.4 g of dimethylsulfoxide was stirred overnight. After addition ofan additional 0.8 g of pyridine and 1 g of dimethylsulfoxide, thesolution was stirred an additional 5 hours. Ether (50 mL) was added, andacetamidophenacylpyridinium chloride was collected by filtration. Theacetamidophenacylpyridinium chloride was dissolved in water, thesolution filtered and 1.7 g concentrated HCl was added. After boilingfor one hour, the solution was cooled, acetone was added, and4-aminophenacylpyridinium chloride hydrochloride was collected byfiltration. Two grams of 4-aminophenacylpyridinium chloridehydrochloride was dissolved in 15 g water and 4.5 g of a basic ionexchange resin (Amberlite IRA400-OH) was added. After stirring, theresin was removed by filtration and 4-aminophenacylpyridinium chloridewas collected as an aqueous solution.

A solution of 1.3 g of 4-aminophenacylpyridinium chloride in 25 g ofwater was heated at reflux with 1 g silver nitrite for about 90 minutes.The precipitate was removed by filtration. Five grams of a carbon blackwith a surface area of 200 m2/g and a DBPA of 122 mL/100 g were addedand the mixture was heated to about 80°. Concentrated HCl (0.52 g) wasadded and the dispersion was stirred an additional 1½ hours. Thediazonium salt N₂C₆H₄COCH₂(NC₅H₅)⁺⁺ was formed in situ, which reactedwith the carbon black. The product had attached C₆H₄COCH₂(NC₅H₅)⁺groups.

TABLE I Rubber Formulations Formulation A B C D E F G H I J K L M NNS-116 100 80 70 NS-114 100 20 30 Duradene 715 100 100 Natural Rubber100 100 SBR-1500 100 100 S-1216 100 SL-574 100 RCTO-586 100 TO-587 100CB Product or 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Comparative DTDM0.8 0.8 0.8 ZnO 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Stearic Acid 2 2 2 2 2 2 2 22 2 2 2 2 2 Flexzone 7P 1 1 1 1 1 1 1 1 1 1 1 1 1 1 CBS 1.25 1.25 1.251.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 MBT 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sulfur 1.75 1.75 1.75 1.751.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 Total 159.2 159.2159.2 159.2 159.2 160 159.2 160 159.2 160 159.2 159.2 159.2 159.2

TABLE II Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 161 118 D 4.4121.38 21.54 305 74 44 0.640 0.126 124 153 162 121 D 4.14 — 20.96 278 7354.7 0.642 0.106 137 189 163 122 D 4.18 20.01 20.72 309 74 44.3 0.6340.117 108 139 Comp. 160 D 3.69 — 14.34 257 71 35.7 0.613 0.160 100 100164 118 E 4.20 — 15.07 242 74 46.8 0.455 0.142 81 106 165 121 E 5.66 —15.62 214 77 53.8 0.439 0.135 75 107 166 122 E 4.10 — 14.98 254 74 46.70.416 0.135 73 106 Comp. 160 E 2.89 15.14 24.02 435 70 45.4 0.414 0.178100 100

TABLE III Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 167 121 G 3.6618.21 27.59 472 69 48.0 0.235 0.121 104 101 168 121 H 3.87 19.32 28.16436 71 51.9 0.210 0.102 100 115 169 122 G 3.47 16.60 28.94 516 70 46.00.249 0.111 87 90 170 123 H 3.16 15.57 28.30 518 70 42.6 0.241 0.146 9190 171 124 G 3.55 16.75 29.67 519 71 42.4 0.244 0.155 102 96 Comp. 160 G3.55 17.87 29.56 489 70 47.3 0.257 0.123 100 100 172 121 I 3.42 18.8225.11 386 72 40.7 0.297 0.159 107 116 173 121 J 3.90 21.38 22.72 316 7446.9 0.281 0.143 105 140 174 122 I 3.09 15.41 25.73 464 73 37.2 0.2940.173 91 114 175 122 J 3.85 20.57 21.07 317 74 45.2 0.275 0.135 98 127176 124 I 3.98 18.60 22.40 354 73 35.7 0.279 0.172 90 103 Comp. 160 I2.91 15.76 25.36 438 70 34.7 0.322 0.180 100 100 177 121 E 4.62 — 14.57283 77 44.1 0.365 0.135 66 108 178 121 F 4.11 — 16.15 241 74 49.8 0.4580.130 104 130 179 122 E 3.89 — 16.72 287 74 43.5 0.410 0.140 79 117 180122 F 4.26 — 16.91 257 75 46.3 0.406 0.127 94 139 Comp. 160 E 3.17 16.8820.52 350 72 39.6 0.421 0.161 100 100

TABLE IV Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 181 120 D 3.68 —16.32 278 73 45.3 0.640 0.135 80 93 182 126 D 3.16 16.20 19.55 349 7355.8 0.630 0.122 87 94 183 139 D 3.56 15.87 18.09 334 74 47.1 0.6480.124 98 81 184 140 D 3.02 15.13 19.97 373 72 46.3 0.662 0.135 103 95Comp. 160 D 3.60 16.88 20.58 354 75 39.9 0.622 0.166 100 100 185 120 E3.03 14.74 16.92 334 74 45.7 0.459 0.162 99 94 186 126 E 3.87 — 12.84238 75 49.9 0.460 0.146 84 120 187 139 E 3.30 — 14.76 296 75 46.4 0.3960.137 63 100 188 140 E 2.41 11.60 18.34 428 72 45.5 0.409 0.170 70 101Comp. 160 E 3.15 — 15.06 283 73 44.1 0.468 0.163 100 100

TABLE V Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 189 123 K 4.8518.31 18.56 312 65 30.2 0.373 0.168 85 99 190 134 K 3.87 15.50 20.65 38364 25.8 0.395 0.177 89 66 Comp. 159 K 4.01 17.03 19.64 336 62 27.3 0.4500.176 100 100 191 123 E 4.25 — 15.07 260 62 32.3 0.375 0.175 88 110 192134 E 4.61 18.50 21.80 349 60 29.4 0.401 0.198 90 91 Comp. 159 E 4.9619.73 20.66 315 59 30.7 0.430 0.194 100 100 193 123 B 3.62 — 23.33 38669 30.86 0.278 0.141 92 104 Comp. 159 B 3.42 — 23.41 402 69 28.36 0.2970.146 100 100 194 127 B 4.04 — 18.52 294 60 35 0.289 0.137 110 113 Comp.159 B 3.25 14.09 18.36 385 60 28.1 0.327 0.173 100 100 195 136 B 3.61 —20.94 447 62 27.7 — 0.165 59 79 Comp. 159 B 3.53 — 22.08 387 63 24.2 —0.157 100 100 196 136 E 5.10 — 15.57 284 63 26.3 — 0.171 41 74 Comp. 159E 4.54 — 20.56 316 63 21.4 — 0.179 100 100

TABLE VI Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 197 129 C 3.2914.57 19.99 389 75 37.7 0.665 0.142 90 116 198 135 C 3.01 13.66 18.03372 75 43.2 0.648 0.141 89 106 Comp. 160 C 2.85 12.78 19.13 408 74 32.80.668 0.173 100 100 199 129 E 3.24 — 12.90 272 77 36.1 0.405 0.162 80117 200 135 E 4.36 — 11.08 239 79 31.0 0.379 0.165 49 81 Comp. 160 E2.80 13.65 22.23 447 75 33.9 0.448 0.178 100 100

TABLE VII Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 201 155 I 3.5614.91 23.63 468 74 33.8 0.291 0.192 83 85 Comp. 160 I 3.40 15.57 26.95492 74 34.2 0.327 0.201 100 100 202 155 G 2.77 14.19 30.13 567 72 34.10.239 0.129 87 84 Comp. 160 G 3.76 17.91 31.15 504 72 43.2 0.241 0.117100 100 203 155 L 3.77 13.36 19.14 325 75 39.1 0.273 0.124 92 114 Comp.160 L 2.96 13.39 21.22 430 73 37.3 0.300 0.149 100 100 204 155 M 3.2310.31 14.09 420 74 17.9 0.790 0.179 68 73 Comp. 160 M 2.61 9.50 17.64525 71 17.5 0.819 0.246 100 100 205 155 N 3.22 13.19 23.12 536 78 330.332 0.185 104 103 Comp. 160 N 3.83 15.06 19.54 408 80 27.1 0.354 0.225100 100

TABLE VIII Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa MpaMpa Elong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 206 154 A 4.0817.75 22.13 362 63 37.5 0.792 0.173 101 134 207 155 A 3.95 16.96 22.13376 63 37.5 0.814 0.178 95 150 208 156 A 3.74 15.15 15.66 300 62 41.10.785 0.149 86 152 209 157 A 4.02 — 14.59 290 62 37.2 0.776 0.150 72 141210 158 A 3.46 — 16.42 357 61 32.8 0.783 0.180 84 130 Comp. 159 A 3.7615.25 19.94 375 67 24.6 0.777 0.233 100 100 211 154 E 6.08 — 14.39 21263 30.7 0.377 0.160 71 128 212 155 E 6.78 — 12.30 178 66 24.9 0.3250.148 51 91 213 156 E 6.28 — 11.10 175 66 25.2 0.322 0.156 54 100 214157 E 5.90 — 10.62 187 68 23.4 0.309 0.166 47 83 215 158 E 5.95 — 11.06190 66 27.0 0.315 0.168 53 91 Comp. 159 E 4.96 19.73 20.66 315 59 30.70.430 0.194 100 100

TABLE IX Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 216 137 D 4.2122.24 23.04 310 73 44.3 0.591 0.127 94 111 217 138 D 4.11 21.64 26.69323 74 44.0 0.670 0.123 99 111 Comp. 160 D 4.14 — 17.62 268 74 37.50.615 0.141 100 100 218 141 D 3.98 18.90 19.23 305 73 44.9 0.611 0.11894 80 Comp. 160 D 4.05 19.56 22.38 337 72 38.3 0.586 0.142 100 100 219137 E 3.81 — 16.55 251 73 46.3 0.450 0.135 127 141 220 138 E 4.00 —16.16 241 74 46.1 0.440 0.138 114 131 Comp. 160 E 3.74 — 17.56 272 7339.7 0.312 0.157 100 100 221 141 E 4.06 — 13.38 260 75 43.5 0.378 0.15861 75 Comp. 160 E 3.30 17.38 20.65 344 71 42.5 0.481 0.163 100 100

TABLE X Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 222 142 E 3.8218.49 19.75 319 73 42.7 0.488 0.152 76 101 223 143 E 3.49 16.70 18.96332 73 42.2 0.466 0.164 77 108 224 144 E 3.57 17.49 18.68 316 73 42.40.477 0.150 66 120 225 145 E 3.35 17.23 18.56 328 73 41.6 0.531 0.160 6497 Comp. 160 E 3.21 16.19 21.51 377 72 41.2 0.494 0.169 100 100 226 142D 3.68 18.53 22.54 353 72 41.8 0.650 0.118 81 99 227 143 D 3.62 17.8522.62 366 72 43.1 0.664 0.134 89 108 228 144 D 3.68 — 13.36 239 72 44.40.655 0.125 96 105 229 145 D 3.92 — 15.80 259 72 42.9 0.678 0.126 81 99230 146 D 3.72 18.91 22.08 340 72 43.7 0.860 0.128 84 104 231 147 D 3.87— 17.90 285 72 45.1 0.643 0.119 84 109 Comp. 160 D 3.73 17.51 20.16 33673 40.0 0.682 0.155 100 100 232 142 G 3.47 16.49 27.76 489 70 43.3 0.2810.148 74 86 233 145 G 3.44 16.45 27.80 495 70 43.8 0.251 0.145 74 46 234146 G 3.44 16.57 27.53 488 70 44.0 0.248 0.139 72 85 235 147 G 3.8917.81 28.28 478 71 44.4 0.267 0.156 76 92 Comp. 160 G 3.88 18.40 28.78470 71 49.1 0.262 0.146 100 100

TABLE XI Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 236 148 D 3.6518.36 21.30 339 73 43.6 0.603 0.122 120 101 237 149 D 3.60 — 17.24 28773 43.7 0.635 0.124 120 114 238 150 D 3.67 — 15.47 280 73 36.7 0.6470.120 85 76 239 151 D 3.74 17.65 20.99 348 73 38.9 0.618 0.149 133 115240 152 D 3.36 16.50 20.77 358 73 40.1 0.651 0.148 117 94 241 153 D 3.83— 16.08 263 73 51.0 0.589 0.111 104 108 Comp. 160 D 3.76 18.94 20.39 31873 38.4 0.624 0.138 100 100 242 148 E 3.52 15.21 15.87 266 73 49.3 0.4300.136 93 134 243 149 E 3.18 — 15.40 280 73 46.5 0.431 0.145 104 113 244150 E 3.48 — 15:57 292 73 38.4 0.412 0.140 68 95 245 151 E 2.81 14.3519.54 382 71 43.5 0.446 0.172 95 112 246 153 E 4.96 — 10.63 173 78 39.80.406 0.136 53 100 Comp. 160 E 2.79 — 12.87 261 70 45.6 0.462 0.164 100100

TABLE XII Carbon 100% 300% Abrader Abrader Black Modulus Modulus TensileHardness Bound Tan_δ Tan_δ Index Index Ex. Prod. Form. Mpa Mpa MpaElong. Shore A Rubber 0° C. 70° C. 14% Slip 21% Slip 247 119 E 3.63 —14.43 246 74 46.1 0.439 0.142 107 126 248 125 E 3.06 16.33 19.15 342 7240.2 0.446 0.150 111 102 249 130 E 4.38 — 14.69 247 76 42.0 0.439 0.13475 105 250 131 E 3.93 — 17.69 289 74 43.2 0.389 0.136 88 107 251 132 E4.17 — 16.88 266 74 47.4 0.460 0.136 101 177 252 133 E 3.52 — 19.18 31873 43.3 0.475 0.142 103 105 Comp. 160 E 3.26 17.08 22.91 383 71 38.60.439 0.164 100 100 253 119 D 3.70 — 19.08 299 73 45.6 0.691 0.127 109133 254 128 D 3.88 18.01 20.4 333 74 39.4 0.462 0.129 77 110 Comp. 160 D3.41 17.06 20.35 344 73 37.6 0.622 0.152 100 100 255 119 I 3.38 18.822.68 350 72 41.1 0.272 0.151 113 114 256 130 I 3.55 16.93 23.73 396 7137.2 0.293 0.169 104 111 Comp. 160 I 3.09 16.08 23.46 407 71 34.7 0.3270.179 100 100 7% Slip 14% Slip 257 119 G 3.56 17.13 29.20 505 71 37.90.256 0.132 96 105 258 125 G 3.21 15.94 28.87 529 69 37.9 0.249 0.139 9292 259 130 G 3.27 16.55 27.70 505 69 41.5 0.233 0.115 97 106 260 131 G3.20 16.58 29.30 509 69 42.0 0.236 0.123 103 110 261 132 G 3.32 16.6526.82 485 70 43.6 0.250 0.153 103 108 262 133 G 3.19 16.36 28.72 508 6942.4 0.251 0.128 93 93 Comp. 160 G 3.57 18.29 28.09 472 70 41.7 0.2520.127 100 100

Example 269 Preparation of a Carbon Black Product

A cold solution of 3.56 g NaNO₂ in water was added to a solution of 10.2g 4,4′-methylenedianiline, 140 g of water and 19.7 g of concentrated HClthat was stirring in an ice bath. After stirring for about 15 minutes,the resulting solution of the diazonium salt was added to a suspensionof 200 g of a carbon black in 1.6 L of water that was stirring at roomtemperature. The carbon black had a surface area of 55 m2/g and DBPA of46 mL/100 g. After stirring for 1½ hours, the mixture was neutralizedwith NaOH and filtered. The carbon black product was washed with waterand dried in an oven at 125° C. The carbon black product contained0.332% nitrogen after Soxhlet extraction overnight with THF, compared to0.081% nitrogen for the untreated carbon black. Therefore, the carbonblack product had 0.18 mmol/g of attached C₆H₄CH₂C₆H₄NH₂ groups.

1. A carbon black product having an organic group attached to the carbonblack, obtained by a process comprising the step of reacting at leastone diazonium salt with a carbon black in a protic reaction medium,wherein said diazonium salt is generated in situ from a primary amine,the protic medium is an aqueous medium, and the primary amine is anamine of the formula A_(y)ArNH₂, in which: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; afunctional group selected from the group consisting of OR, COR, COOR,OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphatesalt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 2. Thecarbon black product of claim 1, wherein Ar is an aromatic orheteroaromatic radical; y is integer from 1 to the total number of —CHradicals present in the aromatic radical and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of a branched or unbranched C₁-C₂₀ substituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; afunctional group selected from the group consisting of OR, COR, COOR,OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphatesalt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 3. Thecarbon product of claim 1, wherein Ar is an aromatic or heteroaromaticradical; y is an integer from 1 to the total number of —CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂,SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)(NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is1 to 6, and w is 2 to 6; and wherein Ar is optionally furthersubstituted with alkyl(s) and/or halogen(s).
 4. The carbon black productof claim 1, wherein Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is a functional group selected from the group consistingof a branched or unbranched C₁-C₂₀ substituted alkyl, branched orunbranched C₃-C₂₀ unsubstituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl.
 5. A carbon black product,having an aromatic group attached to the carbon black, obtained by aprocess comprising the step of reacting at least one diazonium salt witha carbon black in a protic reaction medium, wherein said aromatic groupis a group of the formula A_(y)Ar, in which: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; afunctional group selected from the group consisting of OR, COR, COOR,OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphatesalt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 6. Thecarbon black product of claim 5, wherein Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted alkynyl, unsubstituted or substituted heteroaryl,unsubstituted or substituted alkylaryl, and unsubstituted or substitutedarylalkyl; a functional group selected from the group consisting of OR,COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; brandied or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 7. Thecarbon black product of claim 5, wherein Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of OR, COR, COOR, OCOR, a carboxylatesalt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR),CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, amonobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻,S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 8. The carbon black product of claim 5,wherein Ar is an aromatic or heteroaromatic radical; y is an integerfrom 1 to the total number of —CH radicals present in the aromaticradical; and A, which can be the same or different when y is greaterthan 1, is a functional group selected from the group consisting of abranched or unbranched C₁-C₂₀ substituted alkyl, branched or unbranchedC₃-C₂₀ unsubstituted alkyl, unsubstituted or substituted alkenyl,unsubstituted or substituted alkynyl, unsubstituted or substitutedheteroaryl, unsubstituted or substituted alkylaryl, and unsubstituted orsubstituted arylalkyl.
 9. The carbon black product of claim 5, whereinAr is an aromatic or heteroaromatic radical; y is an integer from 1 tothe total number of —CH radicals present in the aromatic radical; and A,which can be the same or different when y is greater than 1, isindependently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of a branched orunbranched C₁-C₂₀ substituted alkyl, branched or unbranched C₃-C₂₀unsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted alkynyl, unsubstituted or substituted heteroaryl,unsubstituted or substituted alkylaryl, and unsubstituted or substitutedarylalkyl; a functional group selected from the group consisting of OR,COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups; wherein R and R′, which can be the same or different,are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to
 6. 10. The carbon black product of claim 5, whereinsaid aromatic group is a group of the formula A_(y)Ar, in which: Ar isan aromatic radical selected from the group consisting of phenyl,naphthyl, anthryl, phenanthyl, biphenyl, and pyridyl; y is an integerfrom 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 whenAr is anthryl, phenanthryl, or biphenyl, and 1 to 4 when Ar is pyridyl;and A, which can be the same or different when y is greater than 1, isindependently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of a branched orunbranched C₁-C₂₀ substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl; a functional group selected fromthe group consisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄⁺, CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂,PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, X⁻, PR₃ ⁺X⁻S_(k)R, SOR, and SO₂R; and alinear, branched, aromatic, or cyclic hydrocarbon radical, substitutedwith one or more of said functional groups; wherein R is hydrogen;branched or unbranched C₁-C₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl; orunsubstituted or substituted arylalkyl; k is an integer from 1 to 8; andX⁻ is a halide or an anion derived from a mineral or organic acid. 11.The carbon black product of claim 5, wherein said aromatic group is agroup of the formula A_(y)Ar, in which: Ar is an aromatic radicalselected from the group consisting of phenyl, naphthyl, benzothiazolyl,and benzothiadiazolyl; y is an integer from 1 to 5 when Ar is phenyl, 1to 7 when Ar is naphthyl, 1 to 4 when Ar is benzothiazolyl, and 1 to 3when Ar is benzothiadiazolyl; and A, which can be the same or differentwhen y is greater than 1, is independently a substituent on the aromaticradical selected from: a functional group selected from the groupconsisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl); and alinear, branched, aromatic, or cyclic hydrocarbon radical, substitutedwith one or more of said functional groups; wherein R and R′, which canbe the same or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 12. The carbon blackproduct of claim 5, wherein Ar is an aromatic or heteroaromatic radical;y is an integer from 1 to the total number of —CH radicals present inthe aromatic radical; and A, which can be the same or different when yis greater than 1, is independently a substituent on the aromaticradical selected from: a functional group selected from the groupconsisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, asulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₂H₂, amonobasic or dibasic phosphate salt, PO₃H₂, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′,SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups; whereinR and R′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 13. The carbon blackproduct of claim 12, wherein said aromatic group is a group of theformula A_(y)Ar, in which: Ar is an aromatic radical selected from thegroup consisting of phenyl, naphthyl, anthryl, phenanthyl, biphenyl, andpyridyl; y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Aris naphthyl, 1 to 9 when Ar is anthryl, phenanthryl, or biphenyl, and 1to 4 when Ar is pyridyl; and A, which can be the same or different wheny is greater than 1, is independently a substituent on the aromaticradical selected from: a functional group selected from the groupconsisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺, CNNR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃HNa,PO₃Na₂, N═NR, N₂ ⁺X⁻, X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, and SO₂R; and a linear,branched, aromatic, or cyclic hydrocarbon radical, substituted with oneor more of said functional groups; wherein R is hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; and X⁻ is a halideor an anion derived from a mineral or organic acid.
 14. The carbon blackproduct of claim 12, wherein said aromatic group is a group of theformula A_(y)Ar, in which: Ar is an aromatic radical selected from thegroup consisting of phenyl, benzothiazolyl, and benzothiadiazolyl; y isan integer from 1 to 5 when Ar is phenyl, 1 to 4 when Ar isbenzothiazolyl, and 1 to 3 when Ar is benzothiadiazolyl; and A, whichcan be the same or different when y is greater than 1, is independentlya substituent on the aromatic radical selected from: a functional groupselected from the group consisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SR,SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl); and a linear, branched, aromatic, or cyclichydrocarbon radical, substituted with one or more of said functionalgroups; wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to
 6. 15. A carbon black product comprising a carbonblack and at least one organic group attached to the carbon black,wherein the organic group is an aromatic group of the formula A_(y)Ar,wherein: Ar is an aromatic or heteroaromatic radical; y is an integerfrom 1 to the total number of —CH radicals present in the aromaticradical; and A, which can be the same or different when y is greaterthan 1, is independently a substituent on the aromatic radical selectedfrom: a functional group selected from the group consisting of abranched or unbranched C₁-C₂₀ substituted alkyl, branched or unbranchedC₃-C₂₀ unsubstituted alkyl, unsubstituted or substituted alkenyl,unsubstituted or substituted alkynyl, unsubstituted or substitutedheteroaryl, unsubstituted or substituted alkylaryl, and unsubstituted orsubstituted arylalkyl; a functional group selected from the groupconsisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, asulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₂H₂, amonobasic or dibasic phosphate salt, PO₃H₂, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′,SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid, and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 16. The carbon black product of claim15, wherein: Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofa branched or unbranched C₁-C₂₀ substituted alkyl, unsubstituted orsubstituted alkenyl, unsubstituted or substituted alkynyl, unsubstitutedor substituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl; a functional group selected fromthe group consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN,NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 17. The carbon black product of claim15, wherein: Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofOR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonatesalt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic ordibasic phosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt,N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, aSSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear,branched, aromatic, or cyclic hydrocarbon radical, substituted with oneor more of said functional groups and/or halogen(s); wherein R and R′,which can be the same or different, are hydrogen; branched or unbranchedC₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, or alkynyl;unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 18. Thecarbon black product of claim 15, wherein: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl. 19.The carbon black product of claim 15, wherein: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of OR, COR, COOR, OCOR, a carboxylatesalt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, SO₃ ⁻ salts, NR(COR),CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphate salt, PO₂H₂, amonobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻,S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups; whereinR and R′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X− is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 20. The carbon blackproduct of claim 15, wherein: Ar is an aromatic radical selected fromthe group consisting of phenyl, naphthyl anthryl, phenanthryl, biphenyl,and pyridyl; y is an integer from 1 to the total number of —CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺,CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂,PO₃H₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, andSO₂R; and a linear, branched, aromatic, or cyclic hydrocarbon radical,substituted with one or more of said functional groups; wherein R andR′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid.
 21. The carbon blackproduct of claim 15, wherein: Ar is an aromatic radical selected fromthe group consisting of phenyl, benzothiazolyl, and benzothiadiazolyl; yis an integer from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofS_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl); and alinear, branched, aromatic, or cyclic hydrocarbon radical, substitutedwith one or more of said functional groups; wherein R and R′, which canbe the same or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein X is 1 to 6, z is 1 to 6, and w is 2 to
 6. 22. A carbon blackproduct comprising a carbon black and at least one organic group havinga) an aromatic group and b) a cationic group, wherein at least onearomatic group of the organic group is attached to the carbon black andwherein the organic group is a N-substituted pyridinium group.
 23. Acarbon black product comprising a carbon black and at least one organicgroup ArOH attached to the carbon black, wherein Ar is arylene orheteroarylene.
 24. A carbon black product comprising a carbon black andat least one organic group Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to thecarbon black, wherein Ar and Ar′ are arylene, k is an integer from 1 to8, and q and r are
 0. 25. A carbon black product comprising a carbonblack and at least one organic group Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′attached to the carbon black, wherein Ar and Ar′ are heteroarylene, k isan integer from 1 to 8, and q and r are
 0. 26. A process for preparing acarbon black product having an organic group attached to the carbonblack comprising the step of: reacting at least one diazonium salt witha carbon black in a protic reaction medium, wherein the diazonium saltis generated in situ from the primary amine H₂NArS_(k)ArNH₂ wherein Aris benzothiazolylene and k is
 2. 27. A plastic composition comprising aplastic and the carbon product according to claim
 1. 28. A paper productcomprising paper pulp and the carbon product according to claim
 1. 29. Afiber or textile composition comprising a fiber or textile and thecarbon black product according to claim
 1. 30. An elastomer compositionobtained by mixing at least one elastomer and the carbon black productaccording to claim
 1. 31. The elastomer composition of claim 30, whereinthe elastomer comprises at least one synthetic or natural polymer of1,3-butadiene, styrene, isoprene, isobutylene,2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, or propylene. 32.The elastomer composition of claim 31, further comprising at least oneadditive selected from the group consisting of: a curing agent, acoupling agent, a processing aid, an oil extender, and an antioxidant.33. A cured elastomer composition obtained by curing the elastomercomposition of claim
 30. 34. A rubber composition obtained by mixing arubber and the carbon black product according to claim
 1. 35. The rubbercomposition of claim 34, wherein the rubber comprises a natural rubber,a synthetic rubber, or mixtures or a natural and synthetic rubber. 36.The rubber composition of claim 35, wherein the rubber is selected fromthe group consisting of: copolymers of from about 10 to about 70 percentby weight of styrene and from about 90 to about 30 percent by weight ofbutadiene, polymers of conjugated dienes, and copolymers of conjugateddienes with ethylenic group-containing monomers.
 37. The rubbercomposition of claim 36, wherein the rubber is a rubber selected fromthe group consisting of: polybutadiene, polyisoprene, polychloroprene,and poly(styrene-butadiene).
 38. The rubber composition of claim 37,further comprising at least one additive selected from the groupconsisting of: a curing agent, a coupling agent, a processing aid, anoil extender, and an antioxidant.
 39. A cured rubber compositionobtained by curing the rubber composition of claim
 34. 40. A tire ortire component comprising the elastomer composition of claim
 30. 41. Atire or tire component comprising the rubber composition of claim 34.42. A method of decreasing the tan delta max at 70 deg C. of anelastomer composition comprising the step of combining an elastomer withat least one carbon black product of claim
 1. 43. The method of claim42, further comprising forming the elastomer composition into a tire ortire component.
 44. A method of increasing the abrasion resistance of anelastomer composition comprising the step of combining an elastomer withat least one carbon black product of claim
 1. 45. The method of claim44, further comprising forming the elastomer composition into a tire ortire component.
 46. A carbon black product having attached to the carbonblack an aliphatic group, which is substituted by a functional groupselected from the group consisting of OR, COR, COOR, OCOR, COOLi, COONa,COOK, COO⁻NR₄ ⁺, halogen, NR₂, SO₃H, sulfonate salts, OSO₃H, OSO₃⁻salts, NR(COR), CONR₂, NO₂, PO₃H₂ phosphonate salts, phosphate salts,NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, SSO₃ ⁻ salts, SO₂NRR′ SO₂SR, SNRR′,SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR and SO₂R; wherein R and R′, which are the sameor different, are hydrogen, branched or unbranched C₁-C₂₀ unsubstitutedor substituted alkyl, alkenyl or alkynyl; unsubstituted or substitutedaryl; unsubstituted or substituted heteroaryl; unsubstituted orsubstituted alkylaryl; or unsubstituted or substituted arylalkyl; k isan integer from 1 to 8; X⁻ is a halide or an anion derived from amineral or organic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(x), wherein x is 1 to 6, z is 1to 6 and w is 2 to
 6. 47. A carbon black product having attached to thecarbon black a cyclic group selected from cyclic organic groups,alicyclic hydrocarbon groups and heterocyclic hydrocarbon groups, whichis substituted by a functional group selected from the group consistingof R, OR, COR, COOR, OCOR, carboxylate salts, halogen, CN, NR₂, SO₃H,sulfonate salts, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, PO₃H₂,phosphonate salts, phosphate salts, N═NR, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SSO₃H, SSO₃ ⁻ salts, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,2-dithiolanyl), SORand SO₂R; wherein R and R′, which are the same or different, arehydrogen, branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6 and w is 2 to
 6. 48. An elastomer composition obtained by mixing atleast one elastomer and the carbon black product according to claim 46.49. An elastomer composition obtained by mixing at least one elastomerand the carbon black product according to claim
 47. 50. A fiber ortextile composition comprising a fiber or textile and the carbon blackproduct according to claim
 46. 51. A fiber or textile compositioncomprising a fiber or textile and the carbon black product according toclaim
 47. 52. A plastic composition comprising a plastic and the carbonproduct according to claim
 46. 53. A plastic composition comprising aplastic and the carbon product according to claim
 47. 54. A paperproduct comprising paper pulp and the carbon product according to claim46.
 55. A paper product comprising paper pulp and the carbon productaccording to claim
 47. 56. An aqueous ink comprising an aqueous inksolvent and the carbon black product of claim
 46. 57. An aqueous inkcomprising an aqueous ink solvent and the carbon black product of claim47.
 58. An aqueous coating comprising an aqueous coating solvent and thecarbon black product of claim
 46. 59. An aqueous coating comprising anaqueous coating solvent and the carbon black product of claim 47.